KR20150098062A - 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 to improve light emission efficiency and stability of an element and to extend lifespan of the element, an organic electronic element using the same, and an electronic device thereof. The compound is represented by chemical formula 1, wherein m is a constant in the range of zero and four, and n is a constant in the range of zero and three.

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, Indicating a tendency for the lifetime 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 hole transporting layer or at the interface of the hole transporting layer to lower the color purity, reduce the efficiency, and exhibit a low lifetime.

Also, when a material having a high hole mobility is used to make a low driving voltage, the efficiency tends to decrease. This is because the hole mobility is faster than the electron mobility in a general organic electroluminescent device, resulting in a charge unbalance in the light emitting layer, resulting in a reduction in efficiency and a low lifetime.

Therefore, the light-emission-assisting layer has hole mobility (within a full device blue device driving voltage range) and high T1 (electron block) value for having a proper driving voltage for solving the problems of the hole transport layer and the like , And a wide bandgap. However, this can not be achieved simply by the structural properties of the core of the light-emitting auxiliary layer material, but is possible when the properties of the core and sub-substituents of the material are combined. Therefore, in order to improve the efficiency and lifetime of the organic electronic device, development of a light emitting auxiliary layer material having a high T1 value and a wide band gap is desperately required.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electronic device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting 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.

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

In one aspect, the invention provides compounds represented by the formula:

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

By using the compound according to the present invention, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the device, and can greatly improve the color purity and lifetime of the device.

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

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

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

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

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

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

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

The term "alkenyl group" 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.

The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

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

The terms "aryl group" and "arylene group ", as used in the present invention, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirobifluorene group, or a spirobifluorene group.

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

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

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.

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

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

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

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

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

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

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

1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110, ) Comprising an organic compound layer comprising a compound according to the present invention. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

Also, although not shown, the organic electroluminescent device according to the present invention may further include 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.

The compound according to 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 can be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150, the hole transporting layer 140 and / or the light emitting auxiliary layer 151.

On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- Especially when the optimum combination of energy level and T1 value between the organic layers, intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long lifetime and high efficiency can be achieved at the same time.

As described above, in order to solve the light emission problem in the hole transporting layer in recent organic electroluminescent devices, it is preferable that the light emitting auxiliary layer is formed between the hole transporting layer and the light emitting layer. It is necessary to develop different luminescent auxiliary layers. 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)

Accordingly, in the present invention, by forming the light emitting layer or the light emitting auxiliary layer using the compound represented by the general formula (1), the energy level and T1 value between each organic material layer, the mobility of the material, It is possible to simultaneously improve the lifetime and efficiency of the electric element.

The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.

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

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).

[Chemical Formula 1]

In Formula 1,

m is an integer of 0 to 4, and n is an integer of 0 to 3.

R ¹ and R ² are independently of each other hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to 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 ; An alkenyl group having ₂ to ₂₀ carbon atoms; -L ^a -N (Ar ^a ) (Ar ^b ); A C ₁ to C ₃₀ alkoxyl group; And an aryloxy group having ₆ to ₃₀ carbon atoms. For example, R ¹ and R ² can be, independently of each other, hydrogen, phenyl, propenyl or quinazoline.

Further, adjacent groups of R ¹ and R ² may combine with each other to form at least one ring. Here, R ¹ and R ² which do not form a ring may be respectively defined as defined above.

The ring formed by the adjacent groups may be a C ₃ to C ₆₀ aliphatic ring or a C ₆ to C ₆₀ aromatic ring, a C ₂ to C ₆₀ hetero ring, a C ₃ to C ₆₀ alicyclic ring, And may be a single ring or multiple rings as well as a saturated or unsaturated ring.

L ¹ and L ² independently of one another are a C ₆ to C ₆₀ arylene group; A fluorenylene group; C ₂ to C ₆₀ divalent heterocyclic groups containing at least one hetero atom selected from 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 a divalent aliphatic hydrocarbon group. For example, L ¹ and L ² are each independently selected from the group consisting of phenyl, naphthyl, biphenyl, 9,9-dimethyl-9H-fluorene, phenanthrene, pyridine, quinoline, Dibenzothiophene, dibenzofurane, and the like.

Ar ¹ to Ar ⁵ independently represent a C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to 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 ; An alkenyl group having ₂ to ₂₀ carbon atoms; -L ^a -N (Ar ^a ) (Ar ^b ); A C ₁ to C ₃₀ alkoxyl group; And an aryloxy group having ₆ to ₃₀ carbon atoms. For example, Ar ¹ to Ar ⁵ independently of each other represent phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, deuterium substituted phenyl, t-butylphenyl, methylphenyl, pyridylphenyl, 9,9-dimethyl- , 9,9-diphenyl-9H-fluorene, spirobifluorene, 7,7-diphenyl-7H-benzo [c] fluorene, pyridine, phenylpyrimidine, isoquinoline, benzothiophene, dibenzo Thiophene, dibenzofurane, and the like.

L ^a is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; C ₂ to C ₆₀ divalent heterocyclic groups containing at least one hetero atom selected from 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 a divalent aliphatic hydrocarbon group.

Ar ^a and Ar ^b independently represent a C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to 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 an alkenyl group having ₂ to ₂₀ carbon atoms.

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxyl group, and aryloxy group of R ¹ , R ^2, and Ar ¹ are each independently selected from the group consisting of deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; And an arylalkenyl group having from ₈ to ₂₀ carbon atoms.

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxyl group and aryloxy group of Ar ² to Ar ⁵ are each independently selected from the group consisting of halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; And an arylalkenyl group having from ₈ to ₂₀ carbon atoms.

The arylene group, fluorenylene group, divalent heterocyclic group, divalent fused ring group and divalent aliphatic hydrocarbon group of L ¹ and L ² are each a group selected from the group consisting of deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; -N (Ar ^c ) (Ar ^d ); And an arylalkenyl group having from ₈ to ₂₀ carbon atoms.

Ar ^c and Ar ^d are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P;

L ¹ and L ² in the above formula (1) may be selected from the following structures.

In this structure, Q ¹ can be C (R ³ ) or N and Q ² can be C (R ⁴ ) (R ⁵ ), N (R ⁶ ), S,

R < ³ > is hydrogen; heavy hydrogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; And -N (Ar ^e ) (Ar ^f ), wherein Ar ^e and Ar ^f are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P;

For example, R ³ can be hydrogen, phenyl, diphenylamine or 1-phenyl-1H-indole, and the like.

R ⁴ to R ⁶ are, independently of each other, a C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; And a C ₁ to C ₃₀ alkoxyl group. For example, R ⁴ to R ⁶ may be, independently of each other, methyl or phenyl.

Here, the aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, and more preferably 6 to 30 carbon atoms,

The heterocyclic group may be a heterocycle having 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms,

The arylene group 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 alkyl group may have 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.

     &Lt; Formula 2 > < EMI ID =

     &Lt; Formula 5 > < EMI ID =

     &Lt; Formula 8 > < EMI ID =

     &Lt; Formula 11 > < EMI ID =

     &Lt; Formula 14 > < EMI ID =

     &Lt; Formula 17 > < EMI ID = 18.0 >

In the above Chemical Formulas 2 to 19, Ar ¹ to Ar ⁵ , L ¹ , L ² , R ¹ , R ² , m and n may be defined as defined in Formula 1.

More specifically, the compounds represented by Chemical Formulas 1 to 19 may be any one of the following compounds.

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

In another embodiment, the present invention provides an organic electronic device containing the compound represented by the above formula (1).

The organic electroluminescent device includes a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode and containing a compound represented by Formula 1, wherein the hole injection layer, the hole transport layer, the emission auxiliary layer, and the light emitting layer of the organic material layer Or at least one of the layers. That is, the compound represented by Formula 1 may be used as a material for the hole injection layer, the hole transport layer, the light emission assisting layer, or the light emitting layer.

Specifically, the organic material layer may include one of the compounds represented by Chemical Formulas 2 to 19, and the organic material layer may include at least one compound represented by the individual chemical formula.

More specifically, at least one of the hole injecting layer, the hole transporting layer, the light emitting auxiliary layer, and the light emitting layer may include one of the compounds represented by Chemical Formulas 2 to 19, and the hole injecting layer, the hole transporting layer, , And the light emitting layer may contain at least one compound represented by the above individual formula.

In yet another embodiment, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode; An organic material layer disposed between the first electrode and the second electrode; And a light-efficiency-improvement layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.

In this case, the light-efficiency-improvement layer may include a compound represented by Formula 1. Specifically, the light-efficiency-improvement layer may include one of the compounds represented by Formulas 2 to 19, At least one compound represented by the individual formula may be contained.

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 compound represented by Formula 1 according to the present invention is synthesized by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, but is not limited thereto.

<Reaction Scheme 1>

(Ar ¹ to Ar ⁵ , L ¹ , L ² , R ¹ , R ² , m, and n are the same as defined in Formula 1)

I. Sub  Synthesis of 1

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

<Reaction Scheme 2>

Examples of the synthesis of specific compounds belonging to Sub 1 are as follows.

One. Sub  Synthesis Example of 1-1

<Reaction Scheme 3>

(1) Synthesis example of M 1-I-1

Pd ₂ (dba) ₃ (11.94 g, 13 mmol), 50 (50 mmol) of diphenylamine (73.58 g, 434.8 mmol) as a starting material was dissolved in toluene in a round bottom flask, and then 1-bromo-4-iodobenzene (264.02 g, 869.6 mmol) % P ( t- Bu) ₃ (17 ml, 34.8 mmol) and NaO t- Bu (125.37 g, 1304.5 mmol) were added and stirred at 70 ° C. After completion of the reaction, 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 112.78 g (yield: 80%) of the product.

(2) Synthesis of M 1-1 Synthesis Example

Bis (pinacolato) diboron (97.17 g, 382.6 mmol), Pd (dppf) Cl ₂ (8.52 g, 382.6 mmol) was dissolved in a round bottom flask with DMF, 10.4 mmol), KOAc (102.42 g, 1043.6 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 114.95 g (yield: 89%) of the product.

(3) Sub  1-I-1 Synthetic Example

The starting material, phenylboronic acid (105.55g, 865.7mmol) was dissolved in THF to a round bottom flask, 4-bromo-2-iodo -1-nitrobenzene (425.78g, 1298.5mmol), Pd (PPh 3) 4 (50.02g , 43.3 mmol), K ₂ CO ₃ (358.93 g, 2597 mmol) and water 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 168.52 g (yield: 70%) of the product.

(4) Sub  One- II -1 synthesis example

Sub-1-I-1 (168.52 g, 606 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene in a round bottom flask, and then triphenylphosphine (397.35 g, 1514.9 mmol) was added 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 110.36 g (yield: 74%) of the product.

(5) Sub  One- III -1 synthesis example

Sub 1-II-1 (110.36 g, 448.4 mmol) obtained in the above synthesis was dissolved in nitrobenzene in a round bottom flask, iodobenzene (137.23 g, 672.7 mmol), Na ₂ SO _{4 (63.7g, 448.4mmol), K 2} CO 3 (61.98 g, 448.4 mmol) and Cu (8.55 g, 134.5 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 104.03 g (yield: 72%) of the product.

(6) Sub  One- IV -1 synthesis example

After the Sub 1-III-1 (104.03g , 322.9mmol) obtained in the above synthesis in a round bottom flask was dissolved in DMF, Bis (pinacolato) diboron ( 90.19g, 355.2mmol), Pd (dppf) Cl 2 (7.91g, 9.7 mmol), KOAc (95.06 g, 968.6 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 101.34 g (yield: 85%) of the product.

(7) Sub  1-V-1 Synthetic Example

It was dissolved the Sub 1-IV-1 (101.34g , 274.4mmol) obtained in the synthesis as THF in a round bottom flask, 1,3-dibromo-5-chlorobenzene (148.39g, 548.9mmol), Pd (PPh 3) 4 (9.51 g, 8.2 mmol), NaOH (32.93 g, 823.3 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 80.76 g (yield: 68%) of the product.

(8) Sub  One- VI -1 synthesis example

It was dissolved the Sub 1-V-1 (46.13g , 106.6mmol) in THF obtained in the above synthesis in a round bottom flask, M 1-1 (47.49g, 127.9mmol) , Pd (PPh 3) 4 (3.7g, 3.2 mmol), NaOH (12.79 g, 319.8 mmol), water, and the mixture was stirred at 80 ° C. After completion of the reaction, 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 50.92 g (yield: 80%) of the product.

(9) Sub  One- VII -1 synthesis example

After the Sub 1-VI-1 (50.92g , 85.3mmol) obtained in the above synthesis in a round bottom flask was dissolved in DMF, Bis (pinacolato) diboron ( 23.82g, 93.8mmol), Pd (dppf) Cl 2 (2.09g, 2.6 mmol), KOAc (25.11 g, 255.8 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 41.69 g (yield: 71%) of the product.

(10) Sub  1-1 Synthetic Example

It was dissolved the Sub 1-VII-1 (11.72g , 17mmol) obtained in the synthesis as THF in a round bottom flask, 1-bromo-4-iodobenzene (7.22g, 25.5mmol), Pd (PPh 3) 4 (0.98g , 0.9 mmol), K ₂ CO ₃ (7.06 g, 51.1 mmol) and water 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 10.26 g (yield: 84%) of the product.

2. Sub  Synthesis example 1-23

<Reaction Scheme 4>

(1) Synthesis example of M 1-I-12

Pd ₂ (dba) ₃ (6.89 g, 7.5 mmol) and 50% P ( t- Bu) ₃ were added to the starting diphenylamine (42.46 g, 250.9 mmol) 55.32 g (Yield: 68%) of the product was obtained using the M 1 -I-1 synthesis example described above (9.8 ml, 20.1 mmol), NaO t- Bu (72.35 g, 752.7 mmol) and toluene.

(2) M 1-12 Synthesis Example

Bis (pinacolato) diboron (47.66 g, 187.7 mmol), Pd (dppf) Cl ₂ (4.18 g, 5.1 mmol), KOAc (50.24 g, 511.9 mmol) and DMF were obtained 55.12 g (Yield: 87%) of the product using the above M 1-1 synthesis example.

(3) Sub  One- VI -23 synthesis example

(28.68 g, 77.3 mmol), Pd (PPh ₃ ) ₄ (2.23 g, 1.9 mmol) and NaOH (7.73 g, 193.1 mmol) were added to Sub 1-V-1 (27.86 g, 64.4 mmol) mmol), THF, and water were obtained using the Sub 1-VI-1 synthesis example as described above to give 30.57 g (yield: 74%) of the product.

(4) Sub  One- VII -23 synthesis example

Bis (pinacolato) diboron (13.31 g, 52.4 mmol), Pd (dppf) Cl ₂ (1.17 g, 1.4 mmol), KOAc (14.03 g, 142.9 mmol), and 19.69 g (Yield: 60%) of the product were obtained using the Sub 1-VII-1 synthesis example described above.

(5) Sub  1-23 Synthesis Example

1-bromo-3-iodobenzene (12.13 g, 42.9 mmol), Pd (PPh ₃ ) ₄ (1.65 g, 1.4 mmol), K ₂ CO ₃ (11.86 g, 85.8 mmol), THF and water were obtained using the Sub 1-1 Synthesis Example described above to give 14.57 g (yield: 71%) of the product.

3. Sub  Synthesis example 1-33

<Reaction Scheme 5>

1-bromo-2-iodobenzene (14.35 g, 50.7 mmol), Pd (PPh ₃ ) ₄ (1.95 g, 1.7 mmol), K ₂ CO ₃ (14.02 g, 101.4 mmol), THF and water were obtained using the Sub 1-1 Synthesis Example as described above to give 15.77 g (yield: 65%) of the product.

4. Sub  Synthesis example 1-57

<Reaction Scheme 6>

(One) Sub  1-I-57 Synthetic Example

The starting material, phenylboronic acid (70.89g, 581.4mmol) in 4-bromo-1-iodo- 2-nitrobenzene (285.96g, 872.1mmol), Pd (PPh 3) 4 (33.59g, 29.1mmol), K 2 CO 3 (241.07 g, 1744.2 mmol), THF and water were obtained using the Sub 1-I-1 synthesis example described above to give 116.41 g (yield: 72%) of the product.

(2) Sub  One- II -57 Synthetic Example

Triphenylphosphine (274.48 g, 1046.5 mmol) and o- dichlorobenzene were added to Sub 1-I-57 (116.41 g, 418.6 mmol) obtained in the above synthesis using 71.1 g %).

(3) Sub  One- III -57 Synthetic Example

4-iodo-1,1'-biphenyl (30.94 g, 110.4 mmol), Na ₂ SO _{4 (10.46g, 73.6mmol), K 2} CO 3 21.1 g (yield: 73%) of the product was obtained using the Sub 1 -III-1 synthesis example described above with the compound (10.18 g, 73.6 mmol), Cu (1.4 g, 22.1 mmol) and nitrobenzene.

(4) Sub  One- IV -57 Synthetic Example

Bis (pinacolato) diboron (15.02 g, 59.1 mmol), Pd (dppf) Cl ₂ (1.32 g, 1.6 mmol), KOAc (15.83 g, 161.3 mmol) and DMF were obtained 19.87 g (yield: 83%) of the product using the Sub 1-IV-1 synthesis example.

(5) Sub  1-V-57 Synthetic Example

Sub-1 IV-57 obtained in the above Synthesis (19.87g, 44.6mmol) in 1,3-dibromo-5-chlorobenzene ( 24.12g, 89.2mmol), Pd (PPh 3) 4 (1.55g, 1.3mmol), NaOH (5.35 g, 133.8 mmol), THF and water were obtained using the Sub 1-V-1 synthesis example described above to give 15.89 g (Yield: 70%) of the product.

(6) Sub  One- VI -57 Synthetic Example

M 1-1 (13.91 g, 37.5 mmol), Pd (PPh ₃ ) ₄ (1.08 g, 0.9 mmol), NaOH (3.75 g, 93.7 mmol) were added to Sub 1-V-57 (15.89 g, 31.2 mmol) mmol), THF, and water were obtained as 16.19 g (yield: 77%) of the product using the Sub 1-VI-1 synthesis example.

(7) Sub  One- VII -57 Synthetic Example

Bis (pinacolato) diboron (6.72 g, 26.5 mmol), Pd (dppf) Cl ₂ (0.59 g, 0.7 mmol), KOAc (7.08 g, 72.1 mmol) and DMF were obtained 12.51 g (yield: 68%) of the product using the Sub 1-VII-1 synthesis example.

(8) Sub  1-57 Synthetic Example

Bromo-4-iodobenzene (6.94 g, 24.5 mmol), Pd (PPh ₃ ) ₄ (0.95 g, 0.8 mmol), K ₂ CO ₃ (6.78 g, 49.1 mmol), THF and water were obtained using the above Sub 1-1 Synthesis Example, to obtain 10.65 g (yield: 82%) of the product.

5. Sub  Synthesis example 1-72

<Reaction Scheme 7>

(1) M 1-I-5 Synthesis Example

1-bromo-4-iodobenzene (81.36 g, 287.6 mmol), Pd ₂ (dba) ₃ (3.95 g, 4.3 mmol), and di (naphthalen-2-yl) amine (38.73 g, 143.8 mmol) 43.32 g (Yield: 71%) of the product was obtained by using the above M 1 -I-1 synthesis example, using the above M 1 -I-1 synthesis example, P ( t- Bu) ₃ (5.6 ml, 11.5 mmol), NaO t -Bu (41.46 g, 431.4 mmol) ).

(2) Synthesis of M 1-5

Bis (pinacolato) diboron (28.52 g, 112.3 mmol), Pd (dppf) Cl (43.32 g, 102.1 mmol)₂(2.5 g, 3.1 mmol), KOAc (30.06 g, 306.3 mmol) and DMF were obtained 40.91 g (Yield: 85%) of the product using the above M 1-1 synthesis example.

(3) Sub  One- III -72 Synthesis example

3-iododibenzo [ b , d ] thiophene (89.02 g, 287 mmol), Na ₂ SO _{4 (27.18g, 191.3mmol), K 2} CO 3 (26.45 g, 191.3 mmol), Cu (3.65 g, 57.4 mmol), and nitrobenzene were obtained using the above Sub 1-III-1 synthesis example.

(4) Sub  One- IV -72 Synthesis example

Bis (pinacolato) diboron (35.81 g, 141 mmol), Pd (dppf) Cl ₂ (3.14 g, 3.8 mmol), KOAc (37.74 g, 384.6 mmol) and 50.58 g (Yield: 83%) of the product were obtained by using the Sub 1-IV-1 synthesis example described above.

(5) Sub  1-V-72 Synthesis Example

3-dibromo-5-chlorobenzene (57.53 g, 212.8 mmol), Pd (PPh ₃ ) ₄ (3.69 g, 3.2 mmol), NaOH (12.77 g, 319.2 mmol), THF and water, 35.55 g (Yield: 62%) of the product was obtained using the Sub 1-V-1 synthesis example.

(6) Sub  One- VI -72 Synthesis example

The Sub 1-V-72 (35.55g , 66mmol) obtained in the above Synthesis M 1-5 (37.32g, 79.2mmol), Pd (PPh 3) 4 (2.29g, 2mmol), NaOH (7.92g, 197.9mmol) , THF and water were obtained by the synthesis of Sub 1-VI-1 (34.45 g, yield: 65%).

(7) Sub  One- VII -72 Synthesis example

Bis (pinacolato) diboron (11.98 g, 47.2 mmol), Pd (dppf) Cl ₂ (1.05 g, 1.3 mmol), KOAc (12.62 g, 128.6 mmol) and DMF were obtained 24.18 g (yield: 63%) of the product using the Sub 1-VII-1 synthesis example.

(8) Sub  1-72 Synthetic Example

1-bromo-3-iodobenzene (11.47 g, 40.5 mmol), Pd (PPh ₃ ) ₄ (1.56 g, 1.4 mmol) and K ₂ CO ₃ (25 mmol) were added to Sub 1-VII- (11.2 g, 81.1 mmol), THF and water were obtained using the Sub 1-1 Synthesis Example as described above to give 18.72 g (yield: 75%) of the product.

6. Sub  Synthesis example of 1-94

<Reaction Scheme 8>

(One) Sub  1-I-94 Synthetic Example

The starting material, phenylboronic acid (80.05g, 656.5mmol) 1 -bromo-3-iodo-2-nitrobenzene (322.91g, 984.8mmol) _{in, Pd (PPh 3) 4 (} 37.93g, 32.8mmol), K 2 CO 3 (272.21 g, 1969.6 mmol), THF, and water were used to obtain 96.77 g (yield: 53%) of the product using the above Sub 1-I-1 synthesis example.

(2) Sub  One- II -94 Synthesis example

Triphenylphosphine (228.17 g, 869.9 mmol) and o- dichlorobenzene were added to Sub 1-I-94 (96.77 g, 348 mmol) obtained in the above synthesis using 49.17 g (yield: 58% ).

(3) Sub  One- III -94 Synthesis example

Iodobenzene (61.76 g, 302.7 mmol), Na ₂ SO ₄ (31.7 mmol) was added to Sub 1-II-94 (49.67 g, 201.8 mmol) _{(28.67g, 201.8mmol), K 2} CO 3 (27.89g, 201.8mmol), Cu (3.85g, 60.5mmol) and nitrobenzene were obtained using the above Sub 1-III-1 synthesis example.

(4) Sub  One- IV -94 Synthesis example

Bis (pinacolato) diboron (31.57 g, 124.3 mmol), Pd (dppf) Cl ₂ (2.77 g, 3.4 mmol), KOAc (33.28 g, 339.1 mmol) and DMF were obtained 26.71 g (Yield: 64%) of the product using the Sub 1-IV-1 synthesis example.

(5) Sub  1-V-94 Synthesis Example

Sub-1 IV-94 obtained in the above Synthesis (26.71g, 72.3mmol) 1,3-dibromo -5-chlorobenzene in (39.11g, 144.7mmol), Pd ( PPh 3) 4 (2.51g, 2.2mmol), NaOH (8.68 g, 217 mmol), THF and water, 18.78 g (Yield: 60%) of the product was obtained using the Sub 1-V-1 synthesis example.

(6) Sub  One- VI -94 Synthesis example

M 1-1 (19.34 g, 52.1 mmol), Pd (PPh ₃ ) ₄ (1.5 g, 1.3 mmol) and NaOH (5.21 g, 130.2 mmol) were added to Sub 1-V-94 (18.78 g, 43.4 mmol) mmol), THF and water were obtained by using the Sub 1-VI-1 synthesis example described above to give 19.18 g (yield: 74%) of the product.

(7) Sub  One- VII -94 Synthesis example

Bis (pinacolato) diboron (8.97 g, 35.3 mmol), Pd (dppf) Cl ₂ (0.79 g, 1 mmol), KOAc (1 mmol) were added to Sub 1-VI-94 (19.18 g, 32.1 mmol) (9.46 g, 96.4 mmol) and 14.38 g (Yield: 65%) of the product were obtained using the Sub 1-VII-1 synthesis example described above.

(8) Sub  1-94 Synthesis example

1-bromo-4-iodobenzene (8.86 g, 31.3 mmol), Pd (PPh ₃ ) ₄ (1.21 g, 1 mmol) and K ₂ CO ₃ (14.38 g, 20.9 mmol) were added to Sub 1-VII- (8.66 g, 62.6 mmol), THF and water were obtained using the Sub 1-1 Synthesis Example as described above to give 11.99 g (Yield: 80%) of the product.

7. Sub  Synthesis Example of 1-102

<Reaction Scheme 9>

(One) Sub  1-I-102 Synthetic Example

The starting material, phenylboronic acid (61.86g, 507.3mmol) in 1-bromo-2-iodo- 3-nitrobenzene (249.54g, 761mmol), Pd (PPh 3) 4 (29.31g, 25.4mmol), K 2 CO 3 ( 210.36 g, 1522 mmol), THF, and water were obtained in a yield of 79.01 g (Yield: 56%) using the above Sub 1-I-1 synthesis example.

(2) Sub  One- II -102 Synthetic Example

Triphenylphosphine (186.3 g, 710.3 mmol) and o- dichlorobenzene were added to Sub 1-I-102 (79.01 g, 284.1 mmol) obtained in the above synthesis using the above Sub 1-II-1 synthesis example to obtain 41.95 g %).

(3) Sub  One- III -102 Synthetic Example

Sub 1-II-102 obtained in the above Synthesis (41.95g, 170.5mmol) in the 3-iodo-9,9-dimethyl- 9 H -fluorene (81.86g, 255.7mmol), Na 2 SO 4 _{(24.21g, 170.5mmol), K 2} CO 3 (23.56 g, 170.5 mmol), Cu (3.25 g, 51.1 mmol), and nitrobenzene were obtained in a yield of 47.08 g (yield: 63%) using the above Sub 1-III-1 synthesis example.

(4) Sub  One- IV -102 Synthetic Example

Bis (pinacolato) diboron (30 g, 118.1 mmol), Pd (dppf) Cl ₂ (2.63 g, 3.2 mmol), KOAc (31.62 g, 322.2 mmol) and DMF were obtained 40.66 g (Yield: 78%) of the product using the above Sub 1-IV-1 synthesis example.

(5) Sub  1-V-102 Synthesis Example

Sub-1 IV-102 obtained in the above Synthesis (40.66g, 83.8mmol) in 1,3-dibromo-5-chlorobenzene ( 45.29g, 167.5mmol), Pd (PPh 3) 4 (2.9g, 2.5mmol), NaOH (10.05 g, 251.3 mmol), THF and water were used to obtain 29.89 g (yield: 65%) of the product using the Sub 1-V-1 synthesis example.

(6) Sub  One- VI -102 Synthetic Example

To the Sub 1-V-102 (29.89 g, 54.5 mmol) obtained in the above synthesis, M 1-12 (24.26 g, 65.3 mmol), Pd (PPh ₃ ) ₄ (1.89 g, 1.6 mmol) mmol), THF and water were obtained by using the Sub 1-VI-1 synthesis example as described above to give 27.19 g (yield: 70%) of the product.

(7) Sub  One- VII -102 Synthetic Example

Bis (pinacolato) diboron (10.65 g, 41.9 mmol), Pd (dppf) Cl ₂ (0.93 g, 1.1 mmol), KOAc (11.22 g, 114.4 mmol) and DMF were obtained 19.33 g (yield: 63%) of the product using the Sub 1-VII-1 synthesis example.

(8) Sub  1-102 Synthesis Example

1-bromo-3-iodobenzene (10.19 g, 36 mmol), Pd (PPh ₃ ) ₄ (1.39 g, 1.2 mmol) and K ₂ CO ₃ (19.33 g, ₂₄ mmol) were added to Sub 1-VII- 9.96 g, 72.1 mmol), THF, and water were obtained using the above Sub 1-1 Synthesis Example, 13.82 g (yield: 69%) of the product.

8. Sub  Synthesis Example of 1-107

<Reaction formula 10>

(1) M 1-I-24 Synthesis Example

3-bromo-1-iodonaphthalene (157.88 g, 474.2 mmol), Pd ₂ (dba) ₃ (6.51 g, 7.1 mmol) and 50% P ( t- Bu) ₃ were added to the starting diphenylamine (40.12 g, 237.1 mmol) 55.02 g (yield: 62%) of the product was obtained by using the M 1 -I-1 synthesis example described above (9.2 ml, 19 mmol), NaO t- Bu (68.36 g, 711.3 mmol) and toluene.

(2) M 1-24 Synthesis Example

Bis (pinacolato) diboron (41.06 g, 161.7 mmol), Pd (dppf) Cl ₂ (3.6 g, 4.4 mmol), KOAc (43.28 g, 441 mmol) and DMF were obtained 48.93 g (Yield: 79%) of the product using the above M 1-1 synthesis example.

(3) Sub  1-I-107 Synthetic Example

The starting material, naphthalen-1-ylboronic acid (79.53g , 462.4mmol) in 4-bromo-1-iodo- 2-nitrobenzene (227.44g, 693.6mmol), Pd (PPh 3) 4 (26.72g, 23.1mmol), K ₂ CO ₃ (191.73 g, 1387.2 mmol), THF and water were obtained using the above Sub 1-I-1 synthesis example to obtain 109.26 g (yield: 72%) of the product.

(4) Sub  One- II -107 Synthetic Example

Triphenylphosphine (218.32 g, 832.4 mmol) and o- dichlorobenzene were added to Sub 1-I-107 (109.26 g, 332.9 mmol) obtained in the above synthesis using the above Sub 1-II-1 synthesis example to give 69.02 g %).

(5) Sub  One- III -107 Synthetic Example

Sub 1-II-107 obtained in the synthesis iodobenzene (71.32g, 349.6mmol) in _{(69.02g, 233mmol), Na 2} SO 4 _{(33.1g, 233mmol), K 2} CO 3 (32.21 g, 233 mmol), Cu (4.44 g, 69.9 mmol) and nitrobenzene were obtained in the same manner as in Sub 1 -III-1 synthesis example above (yield: 73%).

(6) Sub  One- IV -107 Synthetic Example

Bis (pinacolato) diboron (47.52 g, 187.1 mmol), Pd (dppf) Cl ₂ (4.17 g, 5.1 mmol), KOAc (50.09 g, 510.4 mmol) and DMF were used to obtain 57.07 g (Yield: 80%) of the product using the Sub 1-IV-1 synthesis example.

(7) Sub  1-V-107 Synthesis Example

1,3-dibromo-5-chlorobenzene (73.59 g, 272.2 mmol), Pd (PPh ₃ ) ₄ (4.72 g, 4.1 mmol), NaOH (16.33 g, 408.3 mmol), THF and water, 44.68 g (Yield: 68%) of the product was obtained using the Sub 1-V-1 synthesis example.

(8) Sub  One- VI -107 Synthetic Example

To a Sub 1-V-107 (44.68 g, 92.5 mmol) obtained in the above synthesis, M 1-24 (46.79 g, 111.1 mmol), Pd (PPh ₃ ) ₄ (3.21 g, 2.8 mmol), NaOH (11.11 g, mmol), THF and water were obtained in the same manner as in the Sub 1-VI-1 synthesis example above (yield: 65%).

(9) Sub  One- VII -107 Synthetic Example

Bis (pinacolato) diboron (16.8 g, 66.2 mmol), Pd (dppf) Cl ₂ (1.47 g, 1.8 mmol), KOAc (17.71 g, 180.4 mmol) and DMF were obtained 26.57 g (Yield: 56%) of the product using the Sub 1-VII-1 synthesis example.

(10) Sub  1-107 Synthetic Example

1-bromo-3-iodonaphthalene (16.82 g, 50.5 mmol), Pd (PPh ₃ ) ₄ (1.95 g, 1.7 mmol), K ₂ CO ₃ (13.97 g, 101.1 mmol), THF and water were obtained using the Sub 1-1 Synthesis Example as described above to give 18.71 g (yield: 64%) of the product.

9. Sub  Synthesis Example of 1-109

<Reaction Scheme 11>

(One) Sub  1-I-109 Synthetic Example

4-bromo-1-iodo-2-nitrobenzene (141.41 g, 431.3 mmol), Pd (PPh ₃ ) ₄ (16.61 g, 14.4 mmol), and phenanthren-9-ylboronic acid (63.84 g, 287.5 mmol) K ₂ CO ₃ (119.21 g, 862.5 mmol), THF and water were obtained using the Sub 1-I-1 synthesis example described above to obtain 73.94 g (yield: 68%) of the product.

(2) Sub  One- II -109 Synthesis example

Triphenylphosphine (128.19 g, 488.7 mmol) and o- dichlorobenzene were added to Sub 1-I-109 (73.94 g, 195.5 mmol) obtained in the above synthesis using the above Sub 1-II-1 synthesis example to obtain 42.64 g %).

(3) Sub  One- III -109 Synthesis example

Iodobenzene (37.69 g, 184.7 mmol), Na ₂ SO _{4 ( 2} mL) was added to Sub 1-II-109 (42.64 g, 123.2 mmol) _{(17.49g, 123.2mmol), K 2} CO 3 (27.01 g, 123.2 mmol), Cu (2.35 g, 36.9 mmol), and nitrobenzene were obtained using the above Sub 1-III-1 synthesis example.

(4) Sub  One- IV -109 Synthesis example

Bis (pinacolato) diboron (24.08 g, 94.8 mmol), Pd (dppf) Cl ₂ (2.11 g, 2.6 mmol), KOAc (25.38 g, 258.6 mmol), DMF was obtained 33.18 g (yield: 82%) of the product using the above Sub 1-IV-1 synthesis example.

(5) Sub  1-V-109 Synthesis Example

Sub-1 IV-109 obtained in the above Synthesis (33.18g, 70.7mmol) in 1,3-dibromo-5-chlorobenzene ( 38.22g, 141.4mmol), Pd (PPh 3) 4 (2.45g, 2.1mmol), NaOH (8.48 g, 212.1 mmol), THF, and water were used to obtain 26.74 g (yield: 71%) of the product using the Sub 1-V-1 synthesis example.

(6) Sub  One- VI -109 Synthesis example

M 1-1 (22.36 g, 60.2 mmol), Pd (PPh ₃ ) ₄ (1.74 g, 1.5 mmol) and NaOH (6.02 g, 150.5 mmol) were added to Sub 1-V-109 (26.74 g, mmol), THF, and water were obtained as 25.54 g (yield: 73%) of the product using the Sub 1-VI-1 synthesis example.

(7) Sub  One- VII -109 Synthesis example

Bis (pinacolato) diboron (10.23 g, 40.3 mmol), Pd (dppf) Cl ₂ (0.9 g, 1.1 mmol), KOAc (10.78 g, 109.9 mmol) and DMF were obtained 16.76 g (yield: 58%) of the product using the Sub 1-VII-1 synthesis example.

(8) Sub  1-109 Synthesis Example

1-bromo-4-iodobenzene (9.02 g, 31.9 mmol), Pd (PPh ₃ ) ₄ (1.23 g, 1.1 mmol), K ₂ CO ₃ (8.81 g, 63.7 mmol), THF and water were obtained using the above Sub 1-1 Synthesis Example, 13.38 g (yield: 77%) of the product.

Meanwhile, examples of M 1 are as follows but are not limited thereto, and their FD-MSs are shown in Table 1 below.

[Table 1]

Examples of Sub 1 are as follows but are not limited thereto, and their FD-MSs are shown in Table 2 below.

[Table 2]

II . Sub  Synthesis of 2

Sub 2 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Scheme 12, but is not limited thereto.

<Reaction Scheme 12>

Examples of the synthesis of specific compounds belonging to Sub 2 are as follows.

One. Sub  Synthesis example of 2-1

<Reaction Scheme 13>

The starting material, bromobenzene (26.03g, 165.8mmol) was dissolved in toluene in a round bottom flask, aniline (30.88g, 331.6mmol), Pd 2 (dba) 3 (4.55g, 5mmol), 50% P (t -Bu ) ₃ (6.5 ml, 13.3 mmol) and NaO t- Bu (47.8 g, 497.4 mmol) were added and stirred at 40 ° 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 22.16 g of product (yield: 79%).

2. Sub  Synthesis Example of 2-12

<Reaction Scheme 14>

The starting material, 3-bromo-9,9-dimethyl- 9 H -fluorene (10.41g, 38.1mmol) in aniline (7.1g, 76.2mmol), Pd 2 (dba) 3 (1.05g, 1.1mmol), 50% P ( t- Bu) ₃ (1.5 ml, ₃ mmol), NaO t- Bu (10.99 g, 114.3 mmol) and toluene were used to obtain 8.92 g (yield: 82%) of the product.

3. Sub  2-17

<Reaction Scheme 15>

The starting material, 2-bromo-9,9-dimethyl- 9 H -fluorene isoquinolin-6-amine (12.85g, 89.1mmol) in _{(12.17g, 44.6mmol), Pd 2} (dba) 3 (1.22g, 1.3mmol ), 50% P ( t- Bu) ₃ (1.7 ml, 3.6 mmol), NaO t- Bu (12.85 g, 133.7 mmol) and toluene were used in the Sub 2-1 synthesis example to give 10.49 g %).

4. Sub  Synthesis Example of 2-23

<Reaction Scheme 16>

Aniline (8.44 g, 90.7 mmol), Pd ₂ (dba) ₃ (1.25 g, 1.4 mmol) and 50% P ( t- Bu) were added to the starting material 3-bromodibenzo [ b , d ] thiophene (11.93 g, 45.3 mmol) ) ₃ (1.8 ml, 3.6 mmol), NaO t- Bu (13.07 g, 136 mmol) and toluene were used to obtain 9.36 g (yield: 75%) of the product.

Meanwhile, examples of Sub 2 are as follows but are not limited thereto, and their FD-MSs are shown in Table 3 below.

[Table 3]

III . The final product ( Final Products )

After the Sub 1 (1 eq.) In a round bottom flask was dissolved in toluene, Sub 2 (1 _{eq), Pd 2 (dba) 3} (0.03 _{eq.), P (t -Bu) 3} (0.08 eq.), NaO t -Bu (3 eq) was added and stirred at 100 &lt; 0 &gt; C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column and recrystallization to obtain a final product.

1. Synthesis example of P-1

<Reaction Scheme 17>

Sub 2-1 (1.59 g, 9.4 mmol) and Pd ₂ (dba) ₃ (0.26 g, 0.3 mmol) were dissolved in toluene in a round bottom flask, , 50% P ( t- Bu) ₃ (0.4 ml, 0.8 mmol) and NaO t- Bu (2.71 g, 28.2 mmol) were added and stirred at 100 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 6.28 g (yield: 83%) of the product.

2. Synthesis example of P-40

<Reaction Scheme 18>

Sub 2-17 (3.43 g, 10.2 mmol), Pd ₂ (dba) ₃ (0.28 g, 0.3 mmol) and 50% P ( t- Bu) were added to Sub 1-23 (7.32 g, 10.2 mmol) ₃ (0.4 ml, 0.8 mmol), NaO t- Bu (2.94 g, 30.6 mmol) and toluene were used to obtain 6.05 g of the product (yield: 61%).

3. P-42 Synthesis Example

<Reaction Scheme 19>

Sub 2-23 (3.09 g, 11.2 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.3 mmol) and 50% P ( t- Bu) were added to Sub 1-33 (8.06 g, 11.2 mmol) ₃ (0.4 ml, 0.9 mmol), NaO t- Bu (3.24 g, 33.7 mmol) and toluene were obtained 6.66 g (Yield: 65%) of the product using the above P-1 synthesis example.

4. P-74 Synthesis Example

<Reaction Scheme 20>

Sub 2-12 (2.51 g, 8.8 mmol), Pd ₂ (dba) ₃ (0.24 g, 0.3 mmol) and 50% P ( t- Bu) were added to Sub 1-57 (6.98 g, 8.8 mmol) ₃ (0.3 ml, 0.7 mmol), NaO t- Bu (2.54 g, 26.4 mmol) and toluene were obtained 6.93 g (Yield: 79%) of the product using the above P-1 synthesis example.

5. Synthesis example of P-92

<Reaction Scheme 21>

Sub 2-1 (1.57 g, 9.3 mmol), Pd ₂ (dba) ₃ (0.26 g, 0.3 mmol) and 50% P ( t- Bu) were added to Sub 1-72 (8.59 g, 9.3 mmol) ₃ (0.4 ml, 0.7 mmol), NaO t- Bu (2.68 g, 27.9 mmol) and toluene were obtained 6.78 g (Yield: 72%) of the product using the above P-1 synthesis example.

6. P-117 Synthetic Example

<Reaction Formula 22>

Sub 2-1 (1.72 g, 10.2 mmol), Pd ₂ (dba) ₃ (0.28 g, 0.3 mmol) and 50% P ( t- Bu) were added to Sub 1-94 (7.29 g, 10.2 mmol) 6.55 g (Yield: 80%) of the product was obtained by using the P-1 synthesis example described above, ₃ (0.4 ml, 0.8 mmol), NaO t- Bu (2.93 g, 30.5 mmol)

7. Synthesis example of P-125

<Reaction Scheme 23>

Sub 2-1 (1.55 g, 9.2 mmol), Pd ₂ (dba) ₃ (0.25 g, 0.3 mmol) and 50% P ( t- Bu) were added to Sub 1-102 (7.63 g, 9.2 mmol) _{3 (0.4ml, 0.7mmol), NaO} t -Bu (2.64g, 27.5mmol), the P-1 by the synthesis example 6.24g (yield: 74%) of the product to give the toluene.

8. Synthesis example of P-131

<Reaction Scheme 24>

(1.91 g, 11.3 mmol), Pd ₂ (dba) ₃ (0.31 g, 0.3 mmol) and 50% P ( t- Bu) were added to Sub 1-107 (9.81 g, 11.3 mmol) ₃ (0.4 ml, 0.9 mmol), NaO t- Bu (3.26 g, 33.9 mmol) and toluene were obtained 6.05 g (Yield: 56%) of the product using the above P-1 synthesis example.

9. Synthesis example of P-133

<Reaction Scheme 25>

Sub 2-1 (1.63 g, 9.6 mmol), Pd ₂ (dba) ₃ (0.26 g, 0.3 mmol) and 50% P ( t- Bu) were added to Sub 1-109 (7.86 g, 9.6 mmol) ₃ (0.4 ml, 0.8 mmol), NaO t- Bu (2.77 g, 28.8 mmol) and toluene were obtained 6.71 g (Yield: 77%) of the product using the above P-1 synthesis example.

Meanwhile, the FD-MS values of the compounds P-1 to P-148 of the present invention prepared according to the above Synthesis Examples are shown in Table 4 below.

[Table 4]

On the other hand, in the above Synthesis Example has been described an exemplary composite of the invention, all of Suzuki cross-coupling reaction, PPh ₃ -mediated reductive cyclization reaction (J. Org. Chem. 2005, 70, 5014.), Ullmann reaction, Miyaura boration reaction and Buchwald-Hartwig cross coupling reaction. In addition to the substituents specified in the specific synthesis example, other substituents (Ar ¹ to Ar ⁵ , L ¹ , L ² , R ¹ , R ² , The substitution of the substituent of the substituent of the substituent (s)). For example, in the reaction scheme 2, the reaction of the starting materials → Sub 1-I, Sub 1-IV → Sub 1 → V → Sub 1 → V → Sub VI → Sub 1 → VII → Sub 1 is all Suzuki cross- Sub 1-II -> Sub 1-II reaction in Scheme 2 is based on PPh ₃ -mediated reductive cyclization reaction and Sub 1-II -> Sub 1-III reaction in Scheme 2 is based on Ullmann reaction . Sub 1-III -> Sub 1-IV, Sub 1-VI -> Sub 1-VII and M 1 -I -> M 1 in Scheme 2 are all based on the Miyaura boration reaction and in Scheme 2, -> M 1-I, starting materials in Scheme 12 -> Sub 2 and Scheme 17 through Scheme 25 are based on the Buchwald-Hartwig cross coupling reaction and the reactions will proceed even if substituents not specifically mentioned in these are attached.

Evaluation of manufacturing of organic electric device

[ Example  I-1] green organic electroluminescent device ( Hole transport layer )

An organic electroluminescent device was prepared 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 the hole injection layer was formed, the compound P-1 of the present invention was vacuum deposited on the hole injection layer to a thickness of 60 nm 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 " (2-methyl-8-quinolinolato) aluminum (1, 1'-bisphenyl) -4-oleate) bis hereinafter "BAlq" as abbreviated) was vacuum-deposited to form a hole blocking layer with a thickness of 10nm, on the hole blocking layer of tris (8-quinolinol) aluminum (hereinafter abbreviated as "Alq _3") 40nm 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 .

[ Example  I-2] to [ Example  I-148] green organic electroluminescent device ( Hole transport layer )

Except that one of the compounds P-2 to P-148 of the present invention described in the following Table 5 was used in place of the compound P-1 of the present invention as the hole transporting layer material, organic electroluminescence Device.

[ Comparative Example  I-1]

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

<Comparative Compound 1>

[ Comparative Example  I-2]

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

&Lt; Comparative Compound 2 >

[ Comparative Example  I-3]

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

&Lt; Comparative Compound 3 >

Photoreceptor PR-1 was prepared by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples I-1 to I-148 and Comparative Examples I-1 to I-3 of the present invention. 650, and the T95 lifetime was measured through a lifetime measuring instrument manufactured by Mac Science Inc. 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 the material of the hole transport layer has lower driving voltage than the organic electroluminescent device using Comparative Compounds 1 to 3 as the material of the hole transport layer , Not only the luminous efficiency was improved, but also the lifetime and the like were improved.

These results show that the results are different depending on whether the carbazole core is introduced or not by comparing the compound of the present invention with the comparative compound 2 and the comparative compound 3.

The introduction of a carbazole core into a trivalent phenyl group, which is a linking group connecting -L ¹ -N (Ar ² ) (Ar ³ ) and -L ² -N (Ar ⁴ ) (Ar ⁵ ) Showed a deeper HOMO energy level and a higher T ₁ value than those introduced, and as a result, the device using the compound of the present invention exhibited improved driving voltage, efficiency and lifetime as compared with the device using the comparative compound 2 and the comparative compound 3 .

Thus ^{-L 1 -N (Ar 2) (} Ar 3) and -L ² -N (Ar ⁴⁾ introduction of a carbazole core to trivalent group that connects the connection group (Ar ⁵⁾ the electrons into the high T ₁ value The hole is smoothly transported to the light emitting layer due to the deep HOMO energy level, and as a result, the exciton is more easily generated in the light emitting layer, thereby improving the efficiency and extending the lifetime.

Taken together, the above-described properties (deep HOMO energy level, high T1 value) show that the incorporation of carbazole core can significantly change the bandgap, electrical properties and interface properties, .

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 .

[ Example II -One] Blue organic electroluminescent device  ( The light- )

Organic electroluminescent devices were prepared according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 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 injecting layer, and N, N'-bis (1-naphthalenyl) N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as "NPB") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, Compound P-1 of the present invention was vacuum deposited on the hole transport layer to a thickness of 20 nm to form an emission assist layer, and 9,10-Di (2-naphthyl) anthracene ADN ") as a host material and BD-052X (manufactured by Idemitsu Kosan) as a dopant material were doped at a weight ratio of 93: 7 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 Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example II -2] to [ Example II -78] Blue organic electroluminescent device  ( The light- )

Except that one of the compounds P-2 to P-148 of the present invention described in the following Table 6 was used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material, Thereby preparing a light emitting device.

[ Comparative Example II -One]

An organic electroluminescent device was prepared in the same manner as in Example II-1 except that the following compound 4 was used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material.

<Comparative Compound 4>

[ Comparative Example II -2]

An organic electroluminescent device was prepared in the same manner as in Example II-1, except that the following compound 5 was used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material.

&Lt; Comparative Compound 5 >

[ Comparative Example II -3]

An organic electroluminescent device was prepared in the same manner as in Example II-1 except that no light-emitting auxiliary layer was formed.

Photoresist PR-1 was prepared by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples II-1 to II-78 and Comparative Examples II-1 to II-3 of the present invention. Electroluminescence (EL) characteristics were measured at 650, and T95 lifetime was measured at a 500 cd / m ² standard brightness through a life measuring device manufactured by Mac Science. The measurement results are shown in Table 6 below.

[Table 6]

[ Example III -1] green organic electroluminescent device ( The light- )

Organic electroluminescent devices were prepared according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the glass substrate to form a hole injection layer, and NPB was vacuum-deposited thereon to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Subsequently, the compound P-1 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light-emission-assisting layer, CBP as a host material, Ir (ppy) ₃ as a dopant And doped in a ratio of 90:10 by weight to form a light emitting layer by vacuum evaporation to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is 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 III -2] to [ Example III -123] green organic electroluminescent device ( The light- )

Except that one of the compounds P-2 to P-148 of the present invention described in the following Table 7 was used in place of the compound P-1 of the present invention as the luminescent auxiliary layer material, Thereby preparing a light emitting device.

[ Comparative Example III -One]

An organic electroluminescent device was prepared in the same manner as in Example III-1 except that the compound 4 was used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example III -2]

An organic electroluminescent device was prepared in the same manner as in Example III-1 except that the compound 5 was used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example III -3]

An organic electroluminescent device was prepared in the same manner as in Example III-1 except that no luminescent auxiliary layer was formed.

Photoreceptor PR-1 was prepared by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples III-1 to III-123 and Comparative Examples III-1 to III-3 of the present invention. 650, and the T95 lifetime was measured through a lifetime measuring instrument manufactured by Mac Science Inc. 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  ( The light- )

Organic electroluminescent devices were prepared according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the glass substrate to form a hole injection layer, and NPB was vacuum-deposited thereon to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Subsequently, the compound P-1 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light-emission-assisting layer. Then, CBP was mixed with bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir (acac)") as a dopant material was doped at a weight ratio of 95: 5 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 Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example IV -2] to [ Example IV -99] Red organic electroluminescent device  ( The light- )

Except that one of the compounds P-2 to P-148 of the present invention described in the following Table 8 was used in place of the compound P-1 of the present invention as the luminescent auxiliary layer material, Thereby preparing a light emitting device.

[ Comparative Example IV -One]

An organic electroluminescence device was prepared in the same manner as in Example IV-1, except that the compound 4 was used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example IV -2]

An organic electroluminescence device was prepared in the same manner as in Example IV-1, except that the compound 5 was used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example IV -3]

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

Photoresearch PR-1 was prepared by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples IV-1 to IV-99 and Comparative Examples IV-1 to IV-3 of the present invention. Electroluminescence (EL) characteristics were measured at 650, and the T95 lifetime was measured at a luminance of 2500 cd / m &lt; ² &gt; 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 electroluminescence device using the compound of the present invention as the material of the light-emission-assisting layer has higher luminous efficiency than the organic electroluminescent devices of Comparative Examples II-1 to IV- And the life span was remarkably improved.

It can be confirmed from the results that the device using the comparative compound 4, the comparative compound 5 and the compound of the present invention as a light-emitting auxiliary layer has improved luminous efficiency and lifetime, in particular, Can be confirmed that the compound of the formula (1) exhibits much higher luminous efficiency and life span. The structure in which a carbazole core is introduced into a trivalent phenyl group, which is a linking group connecting -L ¹ -N (Ar ² ) (Ar ³ ) and -L ² -N (Ar ⁴ ) (Ar ⁵ ) This is because the auxiliary layer (blue fluorescence, green phosphorescence, red phosphorescence) acts as a main factor in improving the performance of the device and facilitates charge balance in the light emitting layer due to a deep HOMO energy level and a high T ₁ value .

In addition, Comparative Compound 4 in which -L ¹ -N (Ar ² ) (Ar ³ ) is bonded to a phenylene group to which a carbazole core is bonded shows a high lifetime. However, when the efficiency is compared with the compound of the present invention, Respectively. This indicates that the comparative compound 4 has a relatively high lifetime due to its high blocking ability due to the high T1 value, but the HOMO energy level difference with the host is also large, which means that the efficiency is lower than that of the compound of the present invention.

In other words, the difference between the HOMO energy level of the comparative compound 4 and the HOMO energy level of the host material is larger than the HOMO energy level of the compound of the present invention and the HOMO energy level of the host material, making it difficult for the holes to move relatively, The balance is judged to be reduced.

On the other hand, the compound of the present invention can be obtained by introducing -L ¹ -N (Ar ² ) (Ar ³ ) and -L ² -N (Ar ⁴ ) (Ar ⁵ ) into a trivalent phenyl group to which a carbazole core is bonded, The conjugation length is increased and the bandgap becomes narrower than that of the comparative compound 4, so that it has a sufficiently high T1 value for blocking electrons and a deep HOMO energy level capable of efficient hole transport.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode 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 (9)

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

[In the above formula (1)
m is an integer of 0 to 4, n is an integer of 0 to 3,
R ¹ and R ² are, independently of each other, i) deuterium; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to 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 ; An alkenyl group having ₂ to ₂₀ carbon atoms; -L ^a -N (Ar ^a ) (Ar ^b ); A C ₁ to C ₃₀ alkoxyl group; And an aryloxy group of C ₆ to C ₃₀ ; or ii) adjacent groups may be bonded to each other to form at least one ring (provided that R ¹ and R ² which do not form a ring Is the same as defined in i) above),
L ¹ and L ² independently of one another are a C ₆ to C ₆₀ arylene group; A fluorenylene group; C ₂ to C ₆₀ divalent heterocyclic groups containing at least one hetero atom selected from 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 a divalent aliphatic hydrocarbon group,
Ar ¹ to Ar ⁵ independently represent a C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to 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 ; An alkenyl group having ₂ to ₂₀ carbon atoms; -L ^a -N (Ar ^a ) (Ar ^b ); A C ₁ to C ₃₀ alkoxyl group; And an aryloxy group having from ₆ to ₃₀ carbon atoms,
L ^a is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; C ₂ to C ₆₀ divalent heterocyclic groups containing at least one hetero atom selected from 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 a divalent aliphatic hydrocarbon group,
Ar ^a and Ar ^b independently represent a C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to 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 an alkenyl group having ₂ to ₂₀ carbon atoms.
The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxyl group, and aryloxy group of R ¹ , R ^2, and Ar ¹ are each independently selected from the group consisting of deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to 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
The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxyl group and aryloxy group of Ar ² to Ar ⁵ are each independently selected from the group consisting of halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; And an arylalkenyl group having from ₈ to ₂₀ carbon atoms, which may be substituted with one or more substituents selected from the group consisting of
The arylene group, fluorenylene group, divalent heterocyclic group, divalent fused ring group and divalent aliphatic hydrocarbon group of L ¹ and L ² are each a group selected from the group consisting of deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; ^{-N (Ar c) (Ar d} ) ( wherein, Ar ^c and ^d are independently Ar, C aryl group of ₆ ~ C ₆₀ to each other; fluorenyl group; and O, N, S, at least one of Si and P of A C ₂ to C ₆₀ heterocyclic group containing a hetero atom; And an arylalkenyl group having from ₈ to ₂₀ carbon atoms; The method according to claim 1,
Wherein L &lt; ^{1 &gt;} and L &lt; ^{2 &gt;} are selected from the following structures.

[In the above structure,
Q ¹ is C (R ³ ) or N,
Q ² is C (R ⁴ ) (R ⁵ ), N (R ⁶ ), S or O,
R &lt; ³ &gt; is hydrogen; heavy hydrogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; And ^{-N (Ar e) (Ar f} ) ( wherein, Ar ^e and Ar ^f are, each independently, an aryl group of C ₆ ~ C ₆₀ to each other; fluorenyl group; and O, N, S, at least one of Si and P And a C ₂ to C ₆₀ heterocyclic group containing a heteroatom selected from the group consisting of:
R ⁴ to R ⁶ are, independently of each other, a C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; And a C ₁ to C ₃₀ alkoxyl group; The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
&Lt; Formula 2 &gt;&lt; EMI ID =

&Lt; Formula 5 >< EMI ID =

&Lt; Formula 8 &gt;&lt; EMI ID =

&Lt; Formula 11 >< EMI ID =

&Lt; Formula 14 &gt;&lt; EMI ID =

&Lt; Formula 17 >< EMI ID = 18.0 >

(Wherein Ar ¹ to Ar ⁵ , L ¹ , L ² , R ¹ , R ² , m and n are as defined in claim 1) The method according to claim 1,
Lt; / RTI &gt; is 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 the compound of any one of claims 1 to 4. 6. The method of claim 5,
Wherein the compound is contained in at least one of the hole injection layer, the hole transporting layer, the light emission-assisting layer and the light-emitting layer of the organic material layer. 6. The method of claim 5,
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 first electrode; A second electrode; An organic material layer disposed between the first electrode and the second electrode; And 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,
Wherein the light-efficiency-improvement layer contains a compound according to any one of claims 1 to 4. 6. The method of claim 5,
Wherein the organic electroluminescent device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, or an illumination device.

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