KR20160149879A - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

Provided is a compound which is represented by chemical formula 1. Also, provided is an organoelectric device which comprises a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode. The organic layer includes the compound represented by the chemical formula 1. As the organic layer in the organoelectric device includes the compound represented by chemical formula 1, it is possible to lower driving voltage while increasing luminous efficiency, color purity, and lifespan.

Description

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

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

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

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

Currently, the portable display market is increasing in size as a large-area display, which requires more power than the power consumption required by existing portable displays. Therefore, power consumption is an important factor for portable displays, which have a limited power source, such as a battery, and efficiency and longevity are also important factors to be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage drops and the driving voltage drops. As a result, crystallization of the organic material due to Joule heating, which occurs during driving, And the lifetime tends to increase. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the material are achieved, long life and high efficiency can be achieved at the same time.

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

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

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

When light is emitted from the interface of the hole transporting layer, the color purity and efficiency of the organic electronic device are lowered and the lifetime is shortened. Therefore, it should be a material having a HOMO level between the HOMO energy level of the hole transporting layer and the HOMO energy level of the light emitting layer, and has a high T1 value and a hole mobility (within a driving voltage range of a full device blue device) mobility of the light-emitting layer.

However, this can not be achieved simply by the structural properties of the core of the light-emitting auxiliary layer material, the characteristics of the core and sub-substituent of the light-emitting auxiliary layer material, and the proper combination between the light emitting auxiliary layer, the hole transport layer, A high efficiency and a high number of devices can be realized.

On the other hand, while delaying penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, to the organic layer, stable characteristics such as Joule heating, It is necessary to develop a hole injection / transport layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the lifetime of the device.

In addition, OLED devices are mainly formed by a deposition method, and it is necessary to develop a material that can withstand a long period of time, that is, a material having high heat resistance characteristics.

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

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a compound having efficient electron blocking ability and hole transporting ability, , Color purity and lifetime, and an organic electronic device using the same and an electronic device thereof.

In one aspect, the invention provides compounds represented by the formula: Ar ³ in the formula (1) is represented by the following formula (2), and Ar ⁴ is represented by the following formula (3).

     ≪ Formula 1 >

    &Lt; Formula 2 > < EMI ID =

In another aspect, the present invention provides an organic electronic device using the compound represented by Formula 1 and an electronic device thereof.

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

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

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 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 constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals whenever possible, even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

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

In addition, when an element such as a layer, film, region, plate, or the like is referred to as being "on" or "on" another element, And the like. On the contrary, when an element is referred to as being "directly on " another element, it should be understood that it does not have another element in the middle.

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

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

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

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

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

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

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

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

The term "fluorenyl group" or "fluorenylene group" used in the present invention means a monovalent or divalent functional group in which R, R 'and R & Substituted fluorenyl group "or" substituted fluorenylene group "means that at least one of the substituents R, R 'and R" is a substituent other than hydrogen, and R and R' Together with a spy compound.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, the aryl group or the arylene group includes a single ring, a ring group, a plurality of ring systems bonded together, a spiro compound and the like.

The term "heterocyclic group" as used herein includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group ", but also nonaromatic rings, Means a ring of 2 to 60 rings, but is not limited thereto. The term "heteroatom ", as used herein, unless otherwise indicated, refers to N, O, S, P, or Si, wherein the heterocyclic group includes single ring, ring, And the like.

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

In the present specification, a monovalent or divalent functional group is referred to as a functional group name or a maleic acid is written in front of a parent compound. For example, "divalent benzothiophene" means a divalent functional group of a benzothiophene which is a parent compound, and similarly, "divalent dibenzothiophene" means a divalent functional group of a dibenzothiophene, Furan "refers to the bivalent functional group of the parent compound," bivalent dibenzofuran "refers to the divalent functional group of the dibenzofurane, which is the parent compound, and" bivalent pyrimidine "refers to the bivalent functional group of the parent compound, pyrimidine .

As used herein, the term "ring" includes monocyclic and polycyclic rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom and including aromatic and non-aromatic rings.

As used herein, the term "polycyclic" includes ring assemblies such as biphenyl, terphenyl, and the like, as well as various fused ring systems and spiro compounds, including aromatic as well as non- The ring includes, of course, a heterocycle containing at least one heteroatom.

As used herein, the term "ring assemblies" means that two or more ring systems (a single ring or a fused ring system) are directly connected to each other through a single bond or a double bond, Means that the number of linkages is one less than the total number of rings in the compound. The ring assemblies may be directly connected to each other through a single bond or a double bond.

As used herein, the term " conjugated ring system "refers to a fused ring form shared by at least two atoms, in which the ring system of two or more hydrocarbons is conjugated and contains at least one heteroatom And at least one hetero ring system bonded thereto. Such conjugated ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings or a combination of these rings.

The term "spiro compound" used in the present invention has a 'spiro union', and a spiro connection means a connection in which two rings share only one atom. At this time, atoms shared in two rings are called 'spyro atoms', and they are referred to as 'monospyros,' 'di spyroses,' and 'tri-spyros', depending on the number of spyro atoms contained in a compound. 'Compounds.

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

In addition, a no explicit description, the terms used in this invention in the "unsubstituted or substituted", "substituted" is an alkyl group of deuterium, a halogen, an amino group, a nitrile group, a nitro _{group, C 1 -C 20, C 1} -C ₂₀ alkoxy group, C ₁ -C ₂₀ alkyl amine group, C ₁ -C ₂₀ alkyl thiophene group, C ₆ -C ₂₀ aryl thiophene group, C ₂ -C ₂₀ alkenyl, C ₂ -C of ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron And a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, with the proviso that at least one substituent And is not limited to these substituents.

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

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

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

1, an organic electroluminescent device 100 according to an embodiment of the present invention includes a first electrode 120, a second electrode 180 and a first electrode 120 formed on a substrate 110, And an organic material layer containing a compound according to the present invention is provided between the two electrodes 180. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, etc., and the electron transporting layer 160 may serve as a hole blocking layer You can do it.

Also, although not shown, the organic electroluminescent device according to an embodiment of the present invention further includes a protective layer or 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 can do.

The compound according to one embodiment of the present invention applied to the organic material layer may be a host or a dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, It may be used as a material for the light-efficiency improvement layer. For example, the compound of the present invention can be used as a material for the light emitting layer 150, the hole transporting layer 140 and / or the light emitting auxiliary layer 151, and preferably the material for the hole transporting layer 140 and / .

On the other hand, even if the core is the same core, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at which position, the selection of the core and the combination of the sub- In particular, when the optimal combination of the energy level and T ₁ value between the organic layers, and the intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long life and high efficiency can be achieved at the same time.

As described above, in order to solve the problem of light emission in the hole transporting layer in an organic electroluminescent device, it is preferable that a light-emitting auxiliary layer is formed between the hole transporting layer and the light emitting layer. It is necessary to develop different light-emitting auxiliary layers according to the above.

On the other hand, in the case of the light-emission-assisting layer, it is difficult to deduce the characteristics of the organic layer to be used even if a similar core is used because the relationship between the hole-transport layer and the light-emitting layer (host)

Therefore, in the present invention, by forming the hole transporting layer and / or the light-emitting auxiliary layer by using the compound represented by the general formula (1), the energy level and T ₁ value between each organic material layer, the intrinsic properties (mobility, The lifetime and the efficiency of the organic electronic device can be improved at the same time.

An organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. For example, a metal or a metal oxide having conductivity or an alloy thereof may be deposited on a substrate to form a cathode 120, and a hole injection layer 130 may be formed thereon. A hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170, and then depositing a material that can be used as a cathode 180 on the organic layer. have. Further, a light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

The organic electroluminescent device according to an embodiment of the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The organic electroluminescent device according to an embodiment of the present invention may be one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, or a device for monochromatic or white illumination.

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. 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 compound according to one aspect of the present invention will be described.

A compound according to one aspect of the present invention is represented by the following formula (1).

      &Lt; Formula 1 >

    &Lt; Formula 2 > < EMI ID =

Each symbol described in the above formula can be defined as follows.

Wherein Ar ¹ and Ar ² are independently selected from the group consisting of: i) an aryl group having _{6 to 60} carbon atoms; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; A C ₆ -C ₃₀ aryloxy group; And -L'-N (R ^a ) (R ^b ); or ii) may be bonded to each other to form a ring.

Preferably, Ar ¹ and Ar ² are each independently a C ₆ -C ₆₀ aryl group, a fluorenyl group, a C ₆ group containing at least one hetero atom selected from the group consisting of O, N, S, Si and P ₂ -C ₆₀ heterocyclic ^{group, -L'-N (R a)} (R b) , or the like. Preferably, Ar ¹ and Ar ² independently of each other include at least one hetero atom selected from the group consisting of C ₆ -C ₃₀ aryl groups, fluorenyl groups, O, N, S, Si and P A C ₂ -C ₃₀ heterocyclic group, -L'-N (R ^a ) (R ^b ), and the like. Illustratively, Ar ¹ and Ar ² are independently selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrenyl group, a pyrenyl group, a fluorenyl group, a benzofluorenyl group, a spiropyrrolyl group, , A benzofuryl group, a benzofuryl group, a benzofuryl group, a quinolyl group, an isoquinolyl group, a benzoinodolu group, a dibenzothienyl group, a dibenzofuryl group, a benzocarbazolyl group, a dibenzocarbazolyl group, (R ^a ) (R ^b ) or the like, each of which may be substituted with one or more substituents selected from the group consisting of deuterium, fluoro, cyano, nitro, methoxy, methyl, Which may be further substituted with silane, phenyl, naphthyl, phenanthrene, phenyl substituted with deuterium, fluorene, pyridine, benzofuran, isoquinolane, carbazole, dibenzofuran, dibenzothiophene or naphthobenzothiophene But is not limited thereto.

L 'is a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; Preferably, L 'may be a C ₆ -C ₆₀ arylene group, and may preferably be a C ₆ -C ₃₀ arylene group, and may preferably be a phenylene group, but is not limited thereto .

R ^a and R ^b are independently of each other a C ₆ -C ₆₀ aryl group; A fluorenyl group; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; Preferably, the R ^a and R ^b represent, independently of each other, may be aryl date of C ₆ -C _60, preferably also can be an aryl group of C ₆ -C _30, and preferably may be a phenyl group thereto But is not limited thereto.

Meanwhile, Ar ¹ and Ar ² may combine with each other to form a heterocyclic ring together with N to which they are bonded, and may preferably form a carbazole, benzocarbazole, or dibenzocarbazole ring.

인 경우는 제외한다.In Formula 1, Ar ³ may be represented by Formula 2, and Ar ⁴ may be represented by Formula 3. At this time, the Ar ³

Except for the case of

In Formula 2, X is S or O.

In Formula 3, the A ring and the B ring are independently of each other a C ₆ -C ₁₈ aryl group, preferably phenyl, naphthalene, phenanthrene, and the like. Preferably, the A ring and the B ring are independently of each other, but are not limited thereto.

Here, the mark * indicates a joined portion.

In the general formulas (2) and (3), L ¹ and L ² independently represent a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P, each of which may be selected from the group consisting of (excluding a single bond) heavy hydrogen; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; And an arylalkenyl group having from _{8 to 20} carbon atoms.

Preferably, L ¹ and L ² are, independently of each other, at least one hetero atom selected from the group consisting of a single bond, a C ₆ -C ₆₀ arylene group, a fluorenylene group, O, N, S, and the like group of C ₂ -C ₆₀ hetero ring containing atoms, and preferably, made of a single bond, an arylene group, fluorenyl group, O, N, S, Si and P in the C ₆ -C ₃₀ A C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom selected from the group consisting of C ₁ -C ₃ alkyl, and the like. Illustratively, each of L ¹ and L ² independently represents a single bond, a phenylene group, a biphenylene group, a naphthylene group, a phenanthrenylene group, a fluorenylene group, a pyridylene group, a benzothiophenylene group, a di Benzofuranylene group, dibenzothiophenylene group, and the like, each of which may be further substituted with methyl, phenyl, diphenylamine, etc., but is not limited thereto.

In the general formulas (2) and (3), R ¹ to R ⁴ independently of one another are deuterium; Tritium; A halogen group; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₃₀ . R ¹ to R ⁴ may independently be adjacent to each other to combine with each other to form at least one ring, wherein R ¹ to R ⁴ which do not form a ring are the same as defined above . a is an integer of 0 to 4, b is an integer of 0 to 3, c and d are each an integer of 0 to 8, and when a to d are an integer of 2 or more, a plurality of R ¹ to R ⁴ are the same Can be different.

Preferably, R ¹ to R ⁴ independently of one another are a C ₆ -C ₆₀ aryl group, a C ₂ -C ₆₀ group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P a heterocyclic group, C ₁ -C ₅₀ alkyl group, and the like, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₃₀ of the alkoxyl group, and preferably a C ₆ - alkyl group of C ₃₀ aryl group, O, N, S, Si and P group from the group consisting of at least one C ₂ -C ₃₀ hetero atom containing heterocyclic group _{selected, C 1 -C 20, C 2} -C It may be an alkoxy group of ₂₀ alkenyl groups, C ₁ -C ₂₀ a. Illustratively, R ¹ to R ⁴ independently of each other may be, but not limited to, an ethenylene group, an ethoxy group, a phenyl group, a pyridyl group, a naphthyridinyl group, a dibenzothienyl group, a dibenzofuryl group and the like.

In addition, preferably, R ¹ to R ⁴ may independently form a ring such as naphthyl or phenanthrene together with the benzene ring in which adjacent groups are bonded to each other.

When each of Ar ¹ , Ar ² and R ¹ to R ⁴ is an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryloxy group, halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; -L ' -N (R &apos; ^a ) (R &apos; ^b ); And an arylalkenyl group having from _{8 to 20} carbon atoms.

Specifically, Ar ³ in the formula (1) may be one of the following formulas.

In the above formulas, R ¹ , R ² , L ¹ , X, a and b are the same as defined in the above formulas (1) to (3).

In the above formulas, R ⁷ and R ⁸ independently of one another are deuterium; Tritium; A halogen group; Cyano; A nitro group; A C ₆ -C ₂₀ aryl group; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₂₀ aliphatic ring and a C ₆ -C ₂₀ aromatic ring; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₂₀ alkoxyl group; And an aryloxy group having from _{6 to 20} carbon atoms. R ⁷ and R ⁸ independently of each other may be bonded to each other to form at least one ring, wherein R ⁷ and R ⁸ which do not form a ring are the same as defined above . e is an integer of 0 to 6, f is an integer of 0 to 8, g is an integer of 0 to 5, and when e, f, and g are an integer of 2 or more, a plurality of R ⁷ and R ⁸ are the same Can be different.

Specifically, Ar ⁴ in the formula (1) may be one of the following formulas.

In the above formulas, R ³ , R ⁴ , L ² , c and d are the same as defined in the above formulas (1) to (3).

Specifically, the formula (1) may be represented by one of the following formulas: wherein Ar ¹ and Ar ² are bonded to each other to form a ring.

       &Lt; Formula 4 > < EMI ID =

In Formulas 4 and 5, A ring, B ring, Ar ¹ , Ar ² , R ¹ to R ⁴ , X, L ¹ , L ² , a, b, c and d are as defined in the above formulas same.

In Formula 5, R ⁵ and R ⁶ are each independently selected from the group consisting of deuterium; Tritium; A halogen group; Cyano; A nitro group; A C ₆ -C ₂₀ aryl group; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₂₀ aliphatic ring and a C ₆ -C ₂₀ aromatic ring; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₂₀ alkoxyl group; -L ' -N (R &apos; ^a ) (R &apos; ^b ); And an aryloxy group having from _{6 to 20} carbon atoms. In addition, R ⁵ and R ⁶ independently of each other may bond to each other to form at least one ring, wherein R ⁵ and R ⁶ which do not form a ring are the same as defined above . m and n are each an integer of 0 to 4, and when m and n are an integer of 2 or more, a plurality of R ⁵ and R ⁶ may be the same or different from each other.

Preferably, the R ⁵ and R ⁶ are independently an aryl group of _{C 6 -C 60, O, N} , S, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P to each other a heterocyclic group, alkynyl, -L'-N (R ^a) of the alkyl group of _{C 1 -C 50, C 2 -C} 20 alkenyl, C ₂ -C ₂₀ a (R ^b) and the like, and preferably A C ₆ -C ₃₀ aryl group, a C ₂ -C ₃₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P, a C ₁ -C ₂₀ alkyl group , A C ₂ -C ₂₀ alkenylene group, -L'-N (R ^a ) (R ^b ), and the like. Illustratively, R ⁵ and R ⁶ independently of each other may be a t-butyl group, an ethynyl group, a phenyl group, a pyridyl group, a benzofuryl group, a quinolyl group, a diphenylamine group or the like, each of which is further substituted with deuterium But is not limited thereto.

In addition, preferably, R ⁵ and R ⁶ may form a ring such as naphthyl, phenanthrene, or the like, together with the benzene rings to which the adjacent groups are bonded to each other, independently of each other.

Specifically, the formula (1) may be one of the following compounds.

In another aspect of the present invention, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode; And an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer is at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, and a light emitting layer, May be included. That is, the organic compound layer may be formed of a single compound of the compound represented by the formula (1) or a mixture of two or more compounds. Preferably, the single compound represented by Formula 1 or a mixture containing two or more compounds may be included in the hole transport layer and / or the light emission-assisting layer, or may form these layers.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples 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

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

<Reaction Scheme 1>

I. Synthesis of Sub 1

Sub 1 of Reaction Scheme 1 can be synthesized by the reaction path of Reaction Schemes 2 to 5, but is not limited thereto.

<Reaction Formula 2> When L ¹ and L ² are single bonds

<Reaction Formula 3> When L ¹ and L ² are not a single bond

<Reaction Scheme 4> When L ¹ is not a single bond and L ² is a single bond

<Reaction Scheme 5> When L ¹ is a single bond and L ² is not a single bond

M 1 to M 3 in the above Reaction Schemes 2 to 5 can be synthesized by the reaction path of the following Reaction Schemes 6 to 9, but are not limited thereto.

&Lt; Reaction Scheme 6 > When X is S

<Reaction Scheme 7> When X is O

<Reaction Scheme 8> When L ¹ is a single bond

<Reaction Scheme 9> When L ¹ is not a single bond

<Reaction formula 10>

1. Sub 1-1 Synthetic example

(1) Synthesis of M 1-I-1

The starting material 3-bromo-2- (methylsulfinyl) -1,1'-biphenyl (63.18 g, 214.03 mmol) was added to a round bottom flask with triflic acid (284.1 ml, 3210.47 mmol) and stirred at room temperature for 24 hours Then, pyridine aqueous solution (3750 ml, pyridine: H ₂ O = 1: 5) was slowly added dropwise and refluxed for 30 minutes. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 49.56 g (yield: 88%) of the product.

(2) Synthesis of M 1-1 Synthesis

(32.65 g, 124.07 mmol) obtained in the above synthesis was dissolved in DMF (620 ml) in a round-bottomed flask and then bis (pinacolato) diboron (34.66 g, 136.48 mmol) and Pd (dppf) Cl ₂ 3.04 g, 3.72 mmol), KOAc (36.53 g, 372.22 mmol) was added and stirred at 90 &lt; 0 &gt; C. When the reaction was complete, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 34.64 g (yield: 90%) of the product.

(3) Sub 1-I-1 synthesis

It was dissolved the M 1-1 (64.1g, 206.5mmol) in THF obtained in the above synthesis in a round bottom flask, 1,3,5-tribromobenzene (130g, 413mmol ), Pd (PPh 3) 4 (4.8 g, 4.13 mmol), NaOH (24.8 g, 619.4 mmol), water, and the mixture was stirred at 80 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 58.71 g (yield: 68%) of the product.

(4) Sub 1-1 Synthesis

Sub-1-I-1 (58.6 g, 140.1 mmol), 18-crown-6 (2.5 g, 9.34 mmol) was dissolved in nitrobenzene in a round bottom flask, ), K ₂ CO ₃ (12.9 g, 93.4 mmol) and Cu (5.9 g, 93.4 mmol) were added and stirred at 200 ° C. When the reaction was complete, nitrobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 31.08 g (yield: 60%) of the product.

2. Sub 1-9 Synthetic Example

(1) Synthesis of M 1-I-4

Triflic acid (229 ml, 2585.6 mmol), pyridine aqueous solution (3020 ml, pyridine: H) was added to the starting material, 3-bromo-2- (methylsulfinyl) -1,1 ': 3', 1 " ₂ O = 1: 5) was obtained in a yield of 42.1 g (yield: 72%) using the above M 1 -I-1 synthesis example.

(2) Synthesis of M 1-4

DMF (781 ml), Bis (pinacolato) diboron (34.67 g, 136.5 mmol), Pd (dppf) Cl ₂ (2.72 g, 3.72 mmol), KOAc (36.54 g, 372.3 mmol) was obtained by using the above-mentioned M 1-1 synthesis example, to obtain 40.75 g (Yield: 85%) of the product.

(3) Synthesis of M 2-I-7

2-bromo-1-nitronaphthalene (120 g, 476.1 mmol) and Pd (PPh ₃ ) ₄ (16.5 g, 14.3 mmol) were added to naphthalen-1-ylboronic acid (81.88 g, 476.1 mmol) K ₂ CO ₃ (131.6 g, 952.1 mmol) and water (1047 ml) were added and stirred at 80 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 119.7 g (yield: 84%) of the product.

(4) M 2-7 Synthesis

O-dichlorobenzene (1599 ml) and triphenylphosphine (314.7 g, 1199.7 mmol) were added to M 2 -I-7 (119.7 g, 399.9 mmol) obtained in the above synthesis and stirred at 200 ° C. After the reaction was completed, o-dichlorobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 85.52 g (yield: 80%) of the product.

(5) Sub 1-I-9 synthesis

THF (595ml) in M 1-4 (42g, 104.5mmol) obtained in the synthesis, 1,3,5-tribromobenzene (104.5g, 270.5mmol ), Pd (PPh 3) 4 43.45 g (Yield: 65%) of the product was obtained using the Sub 1-I-1 synthesis example described above (3.1 g, 2.71 mmol), NaOH (16.2 g, 405.8 mmol) and water.

(6) Sub 1-9 Synthesis

Nitrobenzene (292 ml), Sub 1-I-9 (43.3 g, 87.54 mmol), 18-crown-6 (1.5 g, 5.84 mmol), K _{2 CO 3 (8.1g, 58.4mmol),} Cu (3.7g, 58.4mmol) to the Sub synthesis example 1-1 using 25.02g (yield 63%) of product was obtained.

3. Sub 1-18 Synthetic example

(1) Synthesis of M 1-I-11

Triflic acid (287.8 ml, 3252.1 mmol) and pyridine aqueous solution (3798.5 ml, pyridine: H ₂ O = 1: 1) were added to the starting material, 2-bromo-6- (methylsulfinyl) 5) was obtained 42.8 g (yield: 75%) of the product using the above M 1 -I-1 synthesis example.

(2) M 1-11 Synthesis

DMF (794 ml), Bis (pinacolato) diboron (35.24 g, 138.78 mmol), Pd (dppf) Cl ₂ (2.77 g, 3.78 mmol), KOAc (37.14 g, 378.48 mmol) was obtained 33.27 g (Yield: 85%) of the product using the above M 1-1 synthesis example.

 (3) Sub 1-I-18 synthesis

THF (467 ml), 1,3,5-tribromobenzene (82.0 g, 212.26 mmol) and Pd (PPh ₃ ) ₄ (32.9 g, 106.1 mmol) were added to M 1-11 35.5 g (Yield: 80%) of the product was obtained using the Sub 1 -I-1 synthesis example described above (2.5 g, 2.123 mmol), NaOH (12.7 g, 318.4 mmol) and water (467 ml).

(4) Sub 1-18 Synthesis

(35.4 g, 84.774 mmol), 18-crown-6 (1.5 g, 5.65 mmol), K ₂ CO ₃ (0.25 g, 7.8 g, 56.516 mmol) and Cu (3.6 g, 56.516 mmol) were used to obtain 22.80 g (Yield: 80%) of the product using the Sub 1-1 Synthesis Example.

4. Sub 1-30 Synthetic example

(1) Synthesis of M 1-II-18

The starting material, 3-bromo-5- (1,5-naphthyridin-2-yl) - [1,1'-biphenyl] -2-ol (100 g, 265.08 mmol) was added to a round bottom flask with palladium acetate (103 ml, 530.16 mmol) was added to the reaction mixture, and the mixture was stirred at 90 ° C. for 3 hours. After the addition of 3-nitropyridine (3.3 g, 26.5 mmol) and dissolution of the solvent C ₆ H ₆ : DMI = Lt; / RTI &gt; After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 39.78 g (yield: 40%) of the product.

(2) M 1-18 Synthesis

DMF (654 ml), Bis (pinacolato) diboron (29.03 g, 114.33 mmol), Pd (dppf) Cl ₂ (2.28 g, 3.12 mmol), KOAc (30.6 g, 311.81 mmol) was used to obtain 37.31 g (yield: 85%) of the product using the above M 1-1 synthesis example.

(3) Synthesis of M 2-I-3

(1089 ml), 1-bromo-2-nitrobenzene (50 g, 247.5 mmol), Pd (PPh ₃ ) ₄ (8.58 g, 7.425 mmol) and naphthalen-1-ylboronic acid (42.57 g, 247.5 mmol) _{K 2 CO 3 (68.41g, 495.0mmol} ), water (544ml), the M-2-I-7 using the synthetic examples 52.44g (yield 85%) of product was obtained.

(4) M 2-3 Synthesis

O-dichlorobenzene (601.8 ml) and triphenylphosphine (157.8 g, 601.75 mmol) were added to M 2 -I-3 (50 g, 200.58 mmol) obtained in the above synthesis using 34.86 g (yield: 80%).

(5) Sub 1-I-30 synthesis

THF (381.6 ml), 1,3,5-tribromobenzene (67.0 g, 173.4 mmol), and Pd (PPh ₃ ) ₄ (36.6 g, 86.7 mmol) (Yield: 80%) of the product was obtained using the Sub 1-I-1 synthesis example described above (2.0 g, 1.734 mmol), NaOH (10.4 g, 260.154 mmol) and water (381 ml).

(6) Sub 1-30 synthesis

(230.3 ml), Sub 1-I-30 (36.6 g, 69.06 mmol), 18-crown-6 (1.2 g, 4.606 mmol), K ₂ 24.51 g (Yield: 80%) of the product was obtained using the Sub 1-1 Synthesis Example, using CO ₃ (6.4 g, 46.064 mmol) and Cu (2.9 g, 46.064 mmol).

5. Sub 1-33 Synthetic example

(1) Synthesis of M 1-II-21

To the starting material, 2- (4-bromonaphthalen-1-yl) phenol (100 g, 200.586 mmol) was added Palladium acetate (7.5 g, 33.426 mmol), BzOOt- Bu (129.8 ml, 668.516 mmol), 3- nitropyridine 39.73 g (Yield: 40%) of the product was obtained by using the M 1 -II-18 synthesis example as the solvent C ₆ H ₆ : DMI = 3: 2 (1671.3 mL).

(2) Synthesis of M 1-21 Synthesis

DMF (826.8 ml), Bis (pinacolato) diboron (36.66 g, 144.37 mmol), Pd (dppf) Cl ₂ (2.881 g, 3.94 mmol), KOAc (38.642 g, 393.74 mmol) was obtained as a product (38.40 g, Yield 85%) using the above M 1-1 synthesis example.

(3) Sub 1-I-33 synthesis

THF (455.6 ml), 1,3,5-tribromobenzene (80.0 g, 207.088 mmol), Pd (PPh ₃ ) ₄ 37.45 g (Yield: 80%) of the product was obtained using the Sub 1-I-1 synthesis example described above (2.4 g, 2.071 mmol), NaOH (12.4 g, 310.631 mmol) and water (455.6 ml).

(4) Sub 1-33 Synthesis

Nitrobenzene (268.1 ml), Sub 1-I-33 (36.5 g, 80.737 mmol), 18-crown-6 (1.4 g, 5.382 mmol) were added to Carbazole M 2-1 (9.0 g, 53.825 mmol) K ₂ CO ₃ (7.4 g, 53.825 mmol) and Cu (3.4 g, 53.825 mmol) were used to obtain 23.185 g (yield: 80%) of the product using the Sub 1-1 synthesis example.

6. Sub 1- 36 Synthetic Example

(1) Synthesis of M 1-II-24

To the starting material, 2- (3-bromonaphthalen-2-yl) phenol (100 g, 200.586 mmol) was added palladium acetate (7.5 g, 33.426 mmol), BzOOt-Bu (129.8 ml, 668.516 mmol), 3- nitropyridine 39.73 g (Yield: 40%) of the product was obtained by using the M 1 -II-18 synthesis example as the solvent C ₆ H ₆ : DMI = 3: 2 (1671.3 mL).

(2) M 1-24 Synthesis

DMF (826.8 ml), Bis (pinacolato) diboron (36.66 g, 144.37 mmol), Pd (dppf) Cl ₂ (2.881 g, 3.94 mmol), KOAc (38.642 g, 393.74 mmol) was obtained as a product (38.40 g, Yield 85%) using the above M 1-1 synthesis example.

(3) Sub 1-I-36 synthesis

THF (455.6 ml), 1,3,5-tribromobenzene (80.0 g, 207.088 mmol), Pd (PPh ₃ ) ₄ 37.45 g (Yield: 80%) of the product was obtained using the Sub 1-I-1 synthesis example described above (2.4 g, 2.071 mmol), NaOH (12.4 g, 310.631 mmol) and water (455.6 ml).

(4) Sub 1-36 Synthesis

(1.2 g, 4.606 mmol), K ₂ (1.2 g, 4.606 mmol), Sub 1-I-36 (36.6 g, 69.06 mmol) 24.51 g (Yield: 80%) of the product was obtained using the Sub 1-1 Synthesis Example, using CO ₃ (6.4 g, 46.064 mmol) and Cu (2.9 g, 46.064 mmol).

7. Sub 1-39 Synthetic example

(1) Synthesis of M 2-I-2

(1089 ml), 1-bromo-2-nitrobenzene (50 g, 247.5 mmol), Pd (PPh ₃ ) ₄ (8.58 g, 7.425 mmol) and naphthalen-2-ylboronic acid (42.57 g, 247.5 mmol) _{K 2 CO 3 (68.41g, 495.0mmol} ), water (544ml), the M-2-I-7 using the synthetic examples 52.44g (yield 85%) of product was obtained.

(2) Synthesis of M 2-2

O-dichlorobenzene (601.8 ml) and triphenylphosphine (157.8 g, 601.75 mmol) were added to M 2 -I-2 (50 g, 200.58 mmol) obtained in the above synthesis using 34.86 g (yield: 80%).

(3) Synthesis of M 3-I-1

Nitrobenzene (782.4 ml), Sub iodo-4-bromobenzene (66.4 g, 234.731 mmol), 18-crown-6 (4.1 g, 15.649 mmol), K _{2 CO 3 (21.6g, 159.487mmol),} Cu (9.9g, 156.487mmol) the Sub synthesis example 1-1 using 46.60g (yield: 80%) of product was obtained.

(4) Synthesis of M3-1

DMF (778.467 ml), Bis (pinacolato) diboron (34.516 g, 135.92 mmol), Pd (dppf) Cl ₂ (2.712 g, 3.71 mmol), KOAc (36.380 g, 370.7 mmol) was used to obtain 41.45 g (yield: 80%) of the product using the above M 1-1 synthesis example.

(5) Sub 1-39 Synthesis

THF (420.9ml) in Sub 1-I-1 (80.0g , 191.319mmol) obtained in the synthesis, M 3-1 (40.1g, 286.978mmol) , Pd (PPh 3) 4 (Yield: 80%) of the product was obtained using the Sub 1-I-1 synthesis example described above (2.29 g, 1.913 mmol) and NaOH (11.5 g, 286.978 mmol)

8. Sub 1-42 Synthetic example

(1) M 1-I-28 synthesis

Triflic acid (229 ml, 2585.6 mmol) and pyridine aqueous solution (3020 ml, pyridine: H ₂ O = 1: 5) were added to the starting material, 1- (4-bromo-2- (methylsulfinyl) phenyl) naphthalene (64 g, 172.37 mmol) 42.1 g (yield: 72%) of the product was obtained using the M 1 -I-1 synthesis example.

(2) M 1-28 Synthesis

THF (844.8 ml), 4,4'-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2 -yl) -1,1'-biphenyl (108.9g, 268.2mmol), Pd (PPh 3) 4 51.54 g (yield: 75%) of the product was obtained using the Sub 1-I-1 synthesis example described above (4.3 g, 4.023 mmol), NaOH (13.41 g, 335.25 mmol) and water (420.9 ml).

(3) Synthesis of M 2-I-10

2-bromo-3-nitronaphthalene (70 g, 277.7 mmol), Pd (PPh ₃ ) ₄ (9.63 g, 8.331 mmol) and naphthalen-2-ylboronic acid (47.76 g, 277.7 mmol) 70.66 g (Yield: 85%) of the product was obtained by using K ₂ CO ₃ (76.76 g, 555.381 mmol) and water (611 ml) using the M 2 -I-7 synthesis example.

(4) M 2-10 Synthesis

O-dichlorobenzene (701.6 ml) and triphenylphosphine (184.0 g, 701.567 mmol) were added to M 2 -I-10 (70 g, 233.856 mmol) obtained in the above synthesis using 50.0 g (yield: 80%).

(5) Synthesis of M 3-I-4

(935.2 ml), 1-bromo-6-iodonaphthalene (93.4 g, 280.552 mmol), 18-crown-6 (4.9 g, 18.703 mmol), K ₂ CO ₃ (25.9 g, 187.035 mmol) and Cu (11.9 g, 187.035 mmol) were used in the Sub 1-1 Synthesis Example to obtain 49.20 g (yield: 79%) of the product.

(6) M 3-4 Synthesis

DMF (653.5 ml), Bis (pinacolato) diboron (28.975 g, 114.10 mmol), Pd (dppf) Cl ₂ (2.277 g, 3.11 mmol), KOAc (30.540 g, 311.18 mmol) was obtained 43.11 g (Yield: 80%) of the product using the above M 1-1 synthesis example.

(7) Sub 1-I-42 synthesis

THF (455.6ml) in M 1-28 (51.1g, 99.661mmol) obtained in the synthesis, 1,3,5-tribromobenzene (77.0g, 199.322mmol ), Pd (PPh 3) 4 (Yield: 80%) of the product was obtained by using the Sub 1-I-1 synthesis example described above (2.3 g, 1.993 mmol), NaOH (12.0 g, 298.983 mmol) and water (455.6 ml).

(8) Sub 1-42 Synthesis

To the Sub 1-I-42 (49.0 g, 191.319 mmol) obtained in the above synthesis, THF (173.8 ml), M 3-4 (20.5 g, 39.491 mmol), Pd (PPh ₃ ) ₄ (Yield: 82%) of the product was obtained using the sub-1-I-1 synthesis example described above (0.9 g, 0.790 mmol), NaOH (4.7 g, 118.472 mmol) and water (173.8 ml).

9. Sub 1-44 Synthetic example

(1) M 1-30 Synthesis

To 841.8 mL of THF and 2.5-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) dibenzo [b, d] furan (159.6g , 380.02mmol), Pd (PPh 3) 4 (Yield: 75%) of the product was obtained by using the sub-1-I-1 synthesis example described above (6.09 g, 5.7 mmol) and NaOH (19.0 g, 475.025 mmol)

(2) Synthesis of M 3-I-6

To the M 2-4 (50 g, 230.128 mmol) obtained in the above synthesis, nitrobenzene (1150.6 ml), 5-bromo-2-iodopyridine (98.0 g, 345.193 mmol), 18- ₂ CO ₃ (31.8 g, 230.128 mmol) and Cu (14.5 g, 230.128 mmol) were subjected to the synthesis of Sub 1-1 to obtain 70.4 g (yield: 82%) of the product.

(3) M 3-6 Synthesis

DMF (1181.5 ml), Bis (pinacolato) diboron (52.387 g, 206.30 mmol), Pd (dppf) Cl ₂ (4.117 g, 5.63 mmol), KOAc (55.216g, 562.63mmol) was obtained in the form of a product (67.93g, yield: 77%) using the above M 1-1 synthetic example.

(4) Sub 1-I-44 synthesis

THF (698.9 ml), 1,3,5-tribromobenzene (90.0 g, 285.896 mmol) and Pd (PPh ₃ ) ₄ (68.1 g, 142.948 mmol) 65.99 g (Yield: 79%) of the product was obtained by using the Sub 1 -I-1 synthesis example described above (3.3 g, 2.859 mmol) and NaOH (17.2 g, 428.844 mmol) in water (698.9 ml).

(5) Sub 1-44 Synthesis

THF (225.9 ml), M 3-6 (24.1 g, 51.341 mmol), Pd (PPh ₃ ) ₄ (60.0 g, 102.682 mmol) were added to Sub 1-I- (Yield: 80%) of the product was obtained by using the sub-1-I-1 synthesis example described above (1.2 g, 1.027 mmol) and NaOH (6.2 g, 154.023 mmol) in water (225.9 ml).

10. Sub 1-47 Synthetic example

(1) M 1-16 Synthesis

The starting material, 4-bromodibenzo [b, d] furan (60g, 242.83mmol) in DMF (1529.807ml), Bis (pinacolato ) diboron (67.830g, 267.11mmol), Pd (dppf) Cl 2 (5.330 g, 7.28 mmol), KOAc (71.493 g, 728.48 mmol) was obtained 56.43 g (yield: 79%) of the product using the above-mentioned M 1-1 synthesis example.

(2) Synthesis of M 3-I-8

M 2-1 nitrobenzene (1495.1ml) to (50g, 299.025mmol), 1- bromo-3-iodobenzene (126.9g, 448.538mmol), 18-crown-6 (7.9g, 29.903mmol), K 2 CO 3 ( 41.3g, 299.025mmol) and Cu (19.0g, 299.025mmol) were obtained 77.08g (Yield: 80%) of the product using the Sub 1-1 Synthesis Example.

(3) M 3-8 Synthesis

DMF (1173.1 ml), Bis (pinacolato) diboron (52.016 g, 204.84 mmol), Pd (dppf) Cl ₂ (4.088 g, 5.59 mmol), KOAc (54.825 g, 558.64 mmol) was obtained by using the above-mentioned M 1-1 Synthesis Example, to obtain 55.7 g (yield: 81%) of the product.

(4) Sub 1-I-47 synthesis

THF (698.9 ml), 1,3,5-tribromobenzene (100.0 g, 317.662 mmol) and Pd (PPh ₃ ) ₄ (46.7 g, 158.831 mmol) were added to M 1-16 (Yield: 78%) of the product was obtained by using the above Sub 1-I-1 synthesis example in water (698.9 ml) and water (19.1 g, 476.493 mmol) of NaOH (3.7 g, 3.177 mmol)

(5) Sub 1-47 Synthesis

To the obtained Sub 1-I-47 (70.0 g, 174.090 mmol) obtained in the above synthesis, THF (383.0 ml), M 3-8 (32.1 g, 87.045 mmol), Pd (PPh ₃ ) ₄ (Yield: 80%) of the product was obtained using the Sub 1-1 Synthesis Example as described above (2.0 g, 1.741 mmol), NaOH (10.4 g, 261.136 mmol) and water (383.0 ml).

11. Sub 1-49 Synthetic example

(1) Synthesis of M 1-II-34

To the starting material, 6-bromo- [1,1'-biphenyl] -2-ol (100 g, 401.429 mmol) was added Palladium acetate (9.0 g, 40.143 mmol), BzOOt-Bu (155.9 ml, 802.858 mmol), 3-nitropyridine 44.6 g (Yield: 45%) of the product was obtained using the M 1 -II-18 synthesis example described above (5.0 g, 40.143 mmol) and solvent C ₆ H ₆ : DMI = 3: 2 (2007.1 mL).

(2) M 1-34 Synthesis

To a solution of the starting material M 1 -II-34 (44 g, 178.07 mmol) in THF (841.8 ml), 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- (74.454g, 195.88mmol), Pd ( PPh 3) 4 59.88 g (Yield: 80%) of the product was obtained using the sub-1-I-1 synthesis example described above (5.70 g, 5.34 mmol) and NaOH (17.8 g, 445.1 mmol)

(3) Synthesis of M 3-I-10

6-iodo-9,9-dimethyl-9H-fluorene (179.0 g, 448.538 mmol), 18-crown-6 (7.9 g, 98.3128 g (yield: 75%) of the product was obtained using the above Sub 1-1 Synthesis Example, using K ₂ CO ₃ (41.3 g, 299.025 mmol) and Cu (19.0 g, 299.025 mmol).

(4) M 3-10 Synthesis

DMF (1006 ml), Bis (pinacolato) diboron (44.605 g, 175.65 mmol), Pd (dppf) CI ₂ (70 g, 159.68 mmol) (3.505 g, 4.79 mmol), KOAc (47.014 g, 479.05 mmol) was obtained as a product (59.69 g, Yield: 77%) using the above M 1-1 synthesis example.

(5) Sub 1-I-49 synthesis

THF (559.1 ml), 1,3,5-tribromobenzene (80.0 g, 254.130 mmol) and Pd (PPh ₃ ) ₄ (53.4 g, 127.065 mmol) 53.70 g (Yield: 80%) of the product was obtained using the sub-1-I-1 synthesis example described above (2.9 g, 2.541 mmol) and NaOH (15.2 g, 381.184 mmol) and water (559.1 ml).

(6) Sub 1-49 Synthesis

THF (441.4 ml), M 3-10 (24.4 g, 50.167 mmol) and Pd (PPh ₃ ) ₄ (50 g) were added to Sub 1-I- 33.19 g (yield: 82%) of the product was obtained by using the sub-1-I-1 synthesis example described above (1.2 g, 1.03 mmol) and NaOH (6.0 g, 150.50 mmol)

The compound belonging to M 1 may be, but not limited to, the following compounds, and Table 1 shows Field Desorption Mass Spectrometry (FD-MS) values of compounds belonging to M 1.

[Table 1]

The compounds belonging to M 2 and M 3 may be, but not limited to, the following compounds, and Table 2 shows FD-MS values of compounds belonging to M 2 and M 3.

[Table 2]

The compound belonging to Sub 1 may be, but not limited to, the following compounds, and Table 3 shows the FD-MS value of the compound belonging to Sub 1.

[Table 3]

II. Synthetic example of Sub 2

Sub 2 in Scheme 1 may be synthesized by the route of Scheme 8 and Scheme 9 but is not limited thereto.

<Reaction Scheme 11>

(Wherein Hal is Br or Cl).

&Lt; Reaction Formula 12 > When Ar ¹ and Ar ² are bonded to each other to form a ring

1. Sub 2-2 Synthetic example

2- (4-bromophenyl) naphthalene ( 8.3g, 29.3mmol), aniline (2.73g, 29.3mmol), Pd 2 (dba) 3 (1.34g, 1.47mmol), P (t -Bu) 3 (0.59g, , NaO t- Bu (8.45 g, 89.9 mmol) and toluene (308 mL) were added, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 6.06 g (yield: 70%) of the product.

2. Sub 2-8 Synthetic Example

(9.8 g, 28.3 mmol), [1,1'-biphenyl] -4-amine (4.8 g, 28.3 mmol), Pd ₂ (dba), 3- (4-bromophenyl) -9,9- ₃ (1.3 g, 1.42 mmol), P ( t- Bu) ₃ (0.57 g, 2.84 mmol), NaO t- Bu (8.17 g, 85 mmol) and toluene (297 mL) 8.81 g (yield: 68%) of the product was obtained.

3. Sub 2-9 Synthetic example

Pd ₂ (dba) ₃ (1.56 g, 1.7 mmol), P ( t- Bu) ₃ (13.5 g, 34 mmol), aniline (3.16 g, 34 mmol), 2-bromo-9,9- 6.75 g (Yield: 64%) of the product was obtained using the above Sub 2-2 Synthesis Example, using Na2O t- Bu (9.8 g, 101.9 mmol) and toluene (357 mL).

4. Sub 2-25 Synthetic example

(1) Sub 2-I-25 Synthesis Example

2-nitrobenzene (5.8 g, 28.7 mmol), Pd (PPh ₃ ) ₄ (1 g, 0.86 mmol), K ₂ CO ₃ (7.94 g, 57.4 mmol) and water (63 ml), and the mixture was stirred at 80 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 5.43 g (yield: 95%) of the product.

(2) Sub 2-25 Synthetic Example

O- dichlorobenzene (106 ml) and triphenylphosphine (17.45 g, 66.5 mmol) were added to Sub 2-I-25 (5.3 g, 26.6 mmol) obtained in the above synthesis and stirred at 200 ° C. When the reaction was complete, o- dichlorobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 3.65 g (yield: 82%) of the product

5. Sub 2-27 Synthetic Example

(1) Sub 2-I-27 Synthesis Example

The starting material, phenanthren-9-ylboronic acid (6.38g , 28.7mmol) after the dissolved in THF (126ml), 1-bromo -2-nitrobenzene (5.8g, 28.7mmol), Pd (PPh 3) 4 (1g, 0.86 mmol), K ₂ CO ₃ (7.94 g, 57.4 mmol) and water (63 ml) were obtained by using the above Sub 2-I-25 synthesis example.

(2) Sub 2-27 Synthesis Example

After sub-2-I-27 (7.7 g, 25.7 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (103 ml) in a round bottom flask, triphenylphosphine (16.9 g, 64.3 mmol) To obtain 5.43 g (yield: 79%) of the product.

6. Sub 2-42 Synthetic example

2-bromodibenzo [b, d] thiophene (15g, 57mmol), aniline (5.31g, 57mmol), Pd 2 (dba) 3 (2.61g, 2.85mmol), P (t -Bu) 3 (1.15g, 5.7mmol ), NaO t- Bu (16.4 g, 171 mmol), and toluene (598 mL) were obtained by using the Sub 2-2 Synthesis Example described above to give 12.1 g (yield: 77%) of the product.

7. Sub 2-70 Synthetic example

(1) Sub 2-I-70 Synthetic Example

To the starting material, naphthalen-1-ylboronic acid (3.11 g, 25.5 mmol) was added THF (112 ml), 4- (3-bromo-4- nitrophenyl) dibenzo [b, d] furan (9.4 g, 25.5 mmol) 9.23 g (Yield: 87%) of the product was obtained by using the Sub 2-I-25 synthesis example as described in Example 1, except that PPh ₃ ( ₄ ) (0.89 g, 0.77 mmol), K ₂ CO ₃ (7.06 g, 51.1 mmol) .

(2) Sub 2-70 Synthesis Example

O- dichlorobenzene (88 ml) and triphenylphosphine (14.36 g, 54.8 mmol) were added to Sub 2-I-70 obtained in the above synthesis (9.1 g, 21.9 mmol) %).

8. Sub 2-71 Synthetic example

(1) Sub 2-I-71 Synthesis Example

The starting material, naphthalen-2-ylboronic acid (3.05g , 25mmol) in THF (110ml), 2-bromo -1-nitronaphthalene (6.3g, 25mmol), Pd (PPh 3) 4 (0.87g, 0.75mmol), K ₂ CO ₃ (6.91 g, 50 mmol) and water (55 ml) were obtained 6.66 g (Yield: 89%) of the product using the Sub 2-I-25 synthesis example.

(2) Sub 2-71 Synthesis Example

O- dichlorobenzene (87 ml), triphenylphosphine (14.24 g, 54.3 mmol) was added to Sub 2-I-71 obtained in the above synthesis (6.5 g, 21.7 mmol) %).

9. Sub 2-83 Synthetic example

4- (isoquinolin-4-yl) aniline (10g, 45.4mmol), bromobenzene (7.13g, 45.4mmol), Pd 2 (dba) 3 (2.08g, 2.27mmol), P (t -Bu) 3 (0.92g , NaO t- Bu (13.1 g, 136.2 mmol) and toluene (477 mL) were used to obtain 9.15 g (yield: 68%) of the product using the Sub 2-2 synthesis example.

The compounds belonging to Sub 2 may be, but not limited to, the following compounds, and Table 3 shows FD-MS values of the compounds belonging to Sub 2.

[Table 4]

III. Synthesis of Final Product

Sub 1 (1 eq.), Sub 2 (1 eq.), Pd ₂ (dba) ₃ (0.05 eq.), P (t-bu) ₃ (0.1 eq.), NaO t- toluene (10.5 mL / Sub 1 1 mmol) is added and the reaction proceeds at 100 ° C. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain final product.

1. Synthetic examples of 1-8

Sub-1-1 (5.3 g, 10.5 mmol), Sub 2-8 (4.6 g, 10.5 mmol), Pd ₂ (dba) ₃ (0.48 g, 0.53 mmol) and P (t-bu) ₃ NaO t- Bu (3.03 g, 31.5 mmol) and toluene (110 mL) were added, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 6.06 g (yield: 67%) of the product.

2. Synthetic examples of 1-26

Sub-1-22 (7.35 g, 11.2 mmol), Sub 2-26 (2.79 g, 11.2 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.56 mmol) and P (t-bu) ₃ 6.0 g (yield: 65%) of the product was obtained using the above 1-8 Synthesis Example, with NaO t- Bu (3.24 g, 33.7 mmol) and toluene (118 mL)

3. Synthetic examples of 1-29

To a round bottom flask Sub 1-15 (5.82g, 10.5mmol), Sub 2-29 (2.83g, 10.5mmol), Pd 2 (dba) 3 (0.48g, 0.53mmol), P (t-bu) 3 ( NaO t- Bu (3.03 g, 31.5 mmol) and toluene (110 mL) were used to obtain 6.0 g (yield: 77%) of the product using the above 1-8 Synthesis Example.

4. Synthetic examples of 1-38

Sub-1-18 (4.98 g, 9.87 mmol), Sub 2-38 (4.16 g, 9.87 mmol), Pd ₂ (dba) ₃ (0.45 g, 0.49 mmol) and P (t-bu) ₃ NaO t- Bu (2.85 g, 29.6 mmol) and toluene (104 mL) were used to obtain 6.01 g (yield: 72%) of the product using the above 1-8 Synthesis Example.

5. 1- 53 Synthetic Examples

Sub-1-27 (5.64 g, 10.5 mmol), Sub 2-52 (4.04 g, 10.5 mmol), Pd ₂ (dba) ₃ (0.48 g, 0.52 mmol), P (t-bu) ₃ NaO t- Bu (3.02 g, 31.4 mmol) and toluene (110 mL) were used to obtain 6.0 g (Yield: 68%) of the product using the above 1-8 Synthesis Example.

6. 1- 69 Synthetic Examples

Sub-1-32 (5.59 g, 11.4 mmol), Sub 2-68 (4.57 g, 11.4 mmol), Pd ₂ (dba) ₃ (0.52 g, 0.57 mmol), P (t-bu) ₃ 6.5 g (Yield: 65%) of the product was obtained using the above 1-8 Synthesis Example, with NaO t- Bu (3.3 g, 34.3 mmol) and toluene (120 mL).

7. 1-89 Synthetic Examples

To a round bottom flask Sub 1-47 (6.89g, 12.2mmol), Sub 2-83 (3.62g, 12.2mmol), Pd 2 (dba) 3 (0.56g, 0.61mmol), P (t-bu) 3 ( 6.5 g (yield: 63%) of the product was obtained using the above 1-8 Synthesis Example using NaI t- Bu (3.52 g, 36.6 mmol) and toluene (128 mL).

8. 1-91 Synthetic Example

Sub-49 (7.63 g, 9.56 mmol), Sub 2-25 (1.58 g, 9.5 mmol), Pd ₂ (dba) ₃ (0.43 g, 0.47 mmol), P (t-bu) ₃ NaO t- Bu (2.73 g, 28.4 mmol) and toluene (210 mL) were used to obtain 6.0 g (Yield: 71%) of the product.

The FD-MS values of the compounds 1-1 to 1-92 of the present invention prepared according to the above synthesis examples are shown in Table 5 below.

[Table 5]

Evaluation of manufacturing of organic electric device

[Example 1] Green organic electroluminescent device (hole transport layer)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a hole transport layer material. First, 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as" 2-TNATA ") was vacuum deposited on the ITO layer (anode) After forming a hole injection layer, the compound 1-1 of the present invention was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Then, 4,4'-N, N'-dicarbazole-biphenyl (hereinafter abbreviated as "CBP") as a host material and tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) ₃ " (1, 1'-bisphenyl) -4-oleato) bis (2-methyl-8-quinoline oleate ) aluminum (hereinafter referred to as "BAlq" as by vacuum depositing abbreviated) with 10 nm thickness, and forming a hole blocking layer, on the hole blocking layer of tris (8-quinolinol) aluminum (hereinafter referred to as "Alq _3" to the abbreviated ) To 40 Then, an electron injection layer was formed by depositing LiF, which is an alkali metal halide, to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby forming an electron transport layer Thereby preparing an electroluminescent device.

[ Example  2] to [ Example  30] Green organic electroluminescent device  ( Hole transport layer )

An organic electroluminescence device was fabricated in the same manner as in Example 1 except that the compound 1-2 of the present invention described in Table 6 below was used instead of the compound 1-1 of the present invention as the hole transport layer material .

[ Comparative Example  1] to [ Comparative Example  3]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that one of the following Comparative Compounds 1 to 3 was used in place of the compound 1-1 of the present invention as the hole transport layer material.

     &Lt; Comparative Compound 1 > < Comparative Compound 2 > < Comparative Compound 3 &

The organic EL devices manufactured in Examples 1 to 30 and Comparative Examples 1 to 3 of the present invention were subjected to a direct-bias DC voltage and photoluminescence (EL) characteristics And the T95 lifetime was measured using a life measuring apparatus manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 6 below.

[Table 6]

As can be seen from the results of Table 6, when the compound of the present invention is used as a hole transporting layer material of an organic electroluminescent device, the driving voltage is reduced, and the luminous efficiency and lifetime are remarkably improved. In other words, it can be seen that the efficiency and lifetime are generally increased more than those of the comparative compound 1 NPB, which is widely used as a hole transport layer, and the dibenzothiophene having a heterocyclic ring is more preferable than that of Comparative Example 2 having a C- It was confirmed that the driving voltage of Comparative Example 3 was similar but the efficiency was increased by about 117%.

This is because, when the heterocycle (dibenzofuran / dibenzothiophene) is connected to the central phenyl connected to the arylamine and the N-carbazole, instead of the C-carbazole, the efficiency of the comparative compound 3 is higher than that of the comparative compound 2, Since the ring has a high refractive index, it is considered that the efficiency is increased by having a high light transmittance when the device is manufactured. In addition, as the bandgap is widened, the hole transport layer has a proper energy level difference with the light emitting layer, so that the charge balance in the light emitting layer of the hole and electron is increased and the elecetron blocking ability is improved. Thus maximizing the efficiency and life span.

It was confirmed that the compound of the present invention substituted at the 1, 3 and 4 positions of the dibenzothiophene showed better device performance than the comparative compound 3 having the similar structure to the compound of the present invention. When substituted at the 4-position, The best performance was obtained because it has the deepest HOMO. Further, the aromatic ring is further fused to the N-carbazole core or the heterocycle of the compound of the present invention, thereby having a high T1 value and high thermal stability, and it is confirmed that the compound having a condensed aromatic ring has a longer lifetime .

As described above, by further fusing an aromatic ring, the band gap, electrical characteristics, interface characteristics, and the like are largely changed, and it can be confirmed that this acts as a main factor for improving the performance of the device.

Further, in the case of the hole transporting layer, it is necessary to grasp the correlation with the light emitting layer (host), and even if similar cores are used, it is very difficult for the ordinary technologists to deduce the characteristics shown in the hole transporting layer in which the compound according to the present invention is used .

&Lt; Heterocycle number reference >

[Example 31] A blue organic electroluminescent device (luminescent auxiliary layer)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. 2-TNATA was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to a thickness of 60 nm to form a hole injection layer. Then, NPB was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer Respectively. Subsequently, Compound 1-1 of the present invention was vacuum deposited on the hole transport layer to a thickness of 20 nm to form a light emitting auxiliary layer, and 9,10-Di (2-naphthyl) anthracene Doped with BD-052X (manufactured by Idemitsu Kosan) as a host material and doped at a weight ratio of 93: 7 using a dopant material and vacuum-deposited to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq3 was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example  32] to [ Example  62] Blue organic electroluminescent device  ( The light- )

An organic electroluminescent device was produced in the same manner as in Example 31 except that the compound 1-2 of the present invention described in Table 7 was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material Respectively.

[ Comparative Example  4]

An organic electroluminescent device was fabricated in the same manner as in Example 31 except that the light-emitting auxiliary layer material was not used.

[ Comparative Example  5] to [ Comparative Example  6]

An organic electroluminescent device was fabricated in the same manner as in Example 31, except that one of the compounds 2 to 3 was used in place of the compound 1-1 of the present invention as the luminescent auxiliary layer material

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 31 to 62 and Comparative Examples 4 to 6 of the present invention And the T95 lifetime was measured using a life measuring apparatus manufactured by Mac Science Inc. at a luminance of 500 cd / m &lt; 2 &gt;. The measurement results are shown in Table 7 below.

[Table 7]

As can be seen from the results of Table 7, the organic electroluminescence device using the compound of the present invention as the material of the light-emission-assisting layer has a driving voltage slightly higher than that of the organic electroluminescence devices of Comparative Examples 4 to 6, The life span was significantly improved.

It was confirmed that devices using Comparative Compounds 2 to 3 and the compound of the present invention as a light emitting auxiliary layer improved the luminous efficiency and lifetime of the device in which the light emitting auxiliary layer was not formed. And the results are much higher in terms of efficiency and life span.

This is because the amine compound of the present invention having one N-carbazole and one heterocycle (dibenzofuran or dibenzothiophene) in the central phenyl is a main factor for improving the performance of the device in the light-emitting auxiliary layer as well as the hole- This is because it acts as an effective electronic blocking function by maintaining the charge balance. In addition, when a heterocyclic core is provided, since it has a high refractive index, it is considered that the efficiency is increased by having a high light transmittance.

Further, it was confirmed that the compound of the present invention having 1, 3, and 4-membered heterocyclic rings has a longer lifetime than Comparative Compound 3 having the 2-th heterocyclic ring.

The reason why the efficiency of the present invention is improved when the compound of the present invention is used as the luminescent auxiliary layer is that the HOMO energy level of the compound of the present invention is appropriately different from that of the HTL material and therefore the hole is transported more smoothly to the luminescent layer, It is judged that the exciton is more easily generated in the light emitting layer and the efficiency and lifetime are improved. Among them, it can be confirmed that the device using the compound of the present invention having the core in which the 4-position of the heterocycle is bonded to the core and the aromatic ring is further fused is used as a luminescent auxiliary layer, and the luminous efficiency and lifetime of the device are further improved.

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

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are for the purpose of limiting the present invention and are not to be construed as limiting the spirit and scope of the present invention. The scope of protection of the present invention should be construed according to the claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode 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 (12)

A compound represented by the following formula (1):
&Lt; Formula 1 >

&Lt; Formula 2 >< EMI ID =

In Formula 1,
Ar &lt; ^{1 &gt;} and Ar &lt; ^{2 &gt;} are i) independently of each other a C ₆ -C ₆₀ aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; A C ₆ -C ₃₀ aryloxy group; And -L'-N (R ^a ) (R ^b ); or ii) may be bonded to each other to form a ring,
Wherein L 'is a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, and R ^a and R ^b are independently selected from the group consisting of A C ₆ -C ₆₀ aryl group; A fluorenyl group; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P;
Ar ³ is represented by the formula (2), Ar ⁴ is represented by the formula (3)
However, the Ar ³

And,
In formulas (2) and (3)
X is S or O,
The A ring and the B ring are each independently a C ₆ -C ₁₈ aryl group,
L ¹ and L ² are, independently of each other, a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P, each of which is selected from the group consisting of deuterium (excluding a single bond); halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; And an arylalkenyl group having from _{8 to 20} carbon atoms, which may be substituted with at least one substituent selected from the group consisting of
R ¹ to R ⁴ independently of one another are i) deuterium; Tritium; A halogen group; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₃₀ ; or ii) adjacent groups may be bonded to each other to form at least one ring, wherein R ¹ to R ⁴ , which do not form a ring, Is the same as defined in i) above,
a is an integer of 0 to 4, b is an integer of 0 to 3, c and d are each an integer of 0 to 8, and when a to d are an integer of 2 or more, a plurality of R ¹ to R ⁴ are the same Different,
When each of Ar ¹ , Ar ² and R ¹ to R ⁴ is an aryl group, a fluorenyl group, a heterocyclic group, a fused ring group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryloxy group, halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; And an arylalkenyl group having from _{8 to 20} carbon atoms. The method according to claim 1,
Wherein the A ring and the B ring in Formula 1 are independently of each other one of the following formulas:

Here, the mark * indicates a joined portion. The method according to claim 1,
Wherein Ar &lt; ³ &gt; in formula (1) is one of the following formulas:

Wherein R ¹ , R ² , L ¹ , X, a and b are as defined in claim 1,
R ⁷ and R ⁸ independently of one another are i) deuterium; Tritium; A halogen group; Cyano; A nitro group; A C ₆ -C ₂₀ aryl group; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₂₀ aliphatic ring and a C ₆ -C ₂₀ aromatic ring; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₂₀ alkoxyl group; And an aryloxy group of C ₆ -C ₂₀ ; or ii) adjacent groups may be bonded to each other to form at least one ring, wherein R ⁷ and R ⁸ , which do not form a ring, Is the same as defined in i) above,
e is an integer of 0 to 6, f is an integer of 0 to 8, g is an integer of 0 to 5, and when e, f, and g are an integer of 2 or more, a plurality of R ⁷ and R ⁸ are the same It is different. The method according to claim 1,
Wherein Ar &lt; ⁴ &gt; is of the formula: &lt; EMI ID =

In the above formula, R ³ , R ⁴ , L ² , c and d are the same as defined in claim 1. The method according to claim 1,
The compound of formula 1 is represented by one of the following formulas:
&Lt; Formula 4 >< EMI ID =

In Formulas 4 and 5, A ring, B ring, Ar ¹ , Ar ² , R ¹ to R ⁴ , X, L ¹ , L ² , a, b, c and d are the same as defined in the above 1 In addition,
R ⁵ and R ⁶ independently of one another are i) deuterium; Tritium; A halogen group; Cyano; A nitro group; A C ₆ -C ₂₀ aryl group; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of a C ₃ -C ₂₀ aliphatic ring and a C ₆ -C ₂₀ aromatic ring; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₂₀ alkoxyl group; -L &apos; -N (R ' ^a ) (R &apos; ^b ); And an aryloxy group of C ₆ -C ₂₀ ; or ii) adjacent groups may be bonded to each other to form at least one ring, wherein R ⁵ and R ⁶ , which do not form a ring, Is the same as defined in i) above,
m and n are each an integer of 0 to 4, and when m and n are an integer of 2 or more, a plurality of R ⁵ and R ⁶ are the same or different from each other. The method according to claim 1,
A compound characterized by being one of the following compounds:

. A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer contains a compound according to any one of claims 1 to 6. 8. The method of claim 7,
Wherein the compound is contained in at least one layer of the hole injection layer, the hole transport layer, the light emission assisting layer and the light emitting layer of the organic material layer, and the compound is contained as a single kind of compound or a mixture of two or more kinds. device. 8. The method of claim 7,
Further comprising a light-efficiency-improvement layer formed on at least one side of the one surface of the first electrode and the second electrode opposite to the organic material layer. 8. The method of claim 7,
Wherein the organic material 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 including the organic electroluminescent device of claim 7; And a control unit for driving the display device. 12. The method of claim 11,
Wherein the organic electroluminescent device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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