KR102018091B1 - An organic electronic element comprising a layer for improving light efficiency, and an electronic device comprising the same - Google Patents

Abstract

The present invention relates to an organic electric device including a light efficiency improving layer and an electronic device including the same.

Description

Organic electroluminescent device including light efficiency improving layer and electronic device comprising same {AN ORGANIC ELECTRONIC ELEMENT COMPRISING A LAYER FOR IMPROVING LIGHT EFFICIENCY, AND AN ELECTRONIC DEVICE COMPRISING THE SAME}

The present invention relates to an organic electric device including a light efficiency improving layer and an electronic device including the same.

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

The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

The biggest problem for organic electroluminescent devices is life and efficiency. As the display becomes larger, these efficiency and life problems must be solved. Efficiency, lifespan, and driving voltage are related to each other, and as the efficiency increases, the driving voltage is relatively decreased, and as the result, the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. It shows a tendency to increase the life.

However, simply improving the organic material layer does not maximize the efficiency, and the energy level and T1 value of each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of the organic material layer are optimal combinations. When achieved, long life and high efficiency can be achieved simultaneously. Therefore, there is a need for development of a light emitting material having high thermal stability and efficiently achieving a charge balance in the light emitting layer. That is, in order to fully exhibit the excellent characteristics of the organic electric device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric device has not been made sufficiently, and the development of the material of the light emitting layer is particularly urgently required.

On the other hand, it delays the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, and stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.

In recent years, not only studies that improve the device characteristics by changing the performance of each material, but also improve the color purity and efficiency by the optical thickness optimized between the anode and the cathode in the top device of the resonant structure Is one of the important factors to improve. Compared to the bottom device structure of the non-resonant structure, the TOP device structure has a large optical energy loss due to the surface plasmon polariton (SPP) because the formed light is reflected by the anode, which is a reflecting film, and the light is emitted toward the cathode.

Therefore, one of the important methods for improving the shape and efficiency of the EL spectral is to use a light efficiency improving layer for the p-cathode. In general, the electron emission of SPP is mainly used four metals, Al, Pt, Ag, Au, surface plasmon is generated on the surface of the metal electrode. For example, when the cathode is used as Ag, the light emitted by the Ag of the cathode is quenched by the SPP (light energy loss due to Ag), thereby reducing efficiency.

On the other hand, when the light efficiency improving layer is used, SPP is generated at the interface between the MgAg electrode and the high refractive organic material, among which the TE (polarized electric) polarized light disappears in the light efficiency improving layer in the vertical direction by evanescent wave. In addition, TM (transverse magnetic) polarized light moving along the cathode and the light efficiency improving layer causes wavelength amplification by surface plasma resonance, thereby increasing the intensity of the peak. As a result, high efficiency and effective color purity control are possible.

An object of the present invention is to provide an organic electric device including a high refractive index light efficiency improving layer capable of improving high luminous efficiency, low driving voltage, color purity and lifetime of the device, and an electronic device including the same.

In one aspect, the present invention provides an organic electronic device and an electronic device including the compound represented by the following formula in a light efficiency improving layer.

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

1 and 2 are schematic configuration diagrams of an organic electric element according to an embodiment of the present invention.

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

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

"Heterocyclic groups" may also include rings comprising SO ₂ in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.

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

Unless otherwise stated, the term "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.

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

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

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

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definition of the following formulas.

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

1 and 2 are exemplary views of an organic electric device according to an embodiment of the present invention.

1 and 2, an organic electric device according to the present invention includes a first electrode 102, an organic material layer, a second electrode 108, and a light efficiency improving layer 109 formed on a substrate 101. The light efficiency improving layer 109 may be formed under the first electrode (BOTTOM EMISSION method) or / and the second electrode (TOP EMISSION method).

In the case of the top emission method, light formed in the light emitting layer is emitted toward the cathode, and the light emitted toward the cathode passes through the light efficiency improving layer (CPL) formed of organic material having a relatively high refractive index, thereby amplifying the wavelength of light and thus increasing the light efficiency. do.

In the case of a bottom emission method, the light efficiency of the organic electronic device is improved by interposing the light efficiency improving layer according to the present invention.

Of course, the light efficiency improving layer may not be formed only at this position. 1 and 2 illustrate an example in which an optical efficiency improvement layer is formed on an upper portion of the second electrode and a lower portion of the first electrode, respectively, but in FIG. 1, an optical efficiency improvement layer may be formed on the lower portion of the first electrode as well as the upper portion of the second electrode.

1 and 2, examples of the organic material layer include a hole injection layer 103, a hole transport layer 104, a light emitting layer 105, an electron transport layer 106, and an electron injection layer 107. At least one layer may be omitted.

In addition, although not shown, the organic electronic device includes a hole blocking layer (HBL) that prevents the movement of holes, an electron blocking layer (EBL) that prevents the movement of electrons, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located further. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In addition, the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer as well as the light efficiency improving layer.

The organic electroluminescent device according to another embodiment of the present invention is a metal oxide or a metal oxide having a conductivity or a substrate on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation It can be prepared by depositing an alloy of the anode to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer thereon, and then depositing a material that can be used as a cathode thereon have. At this time, the light efficiency improving layer according to the present invention can be formed on the lower or upper anode.

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure.

In addition, the organic material layer and the light efficiency improving layer may use a variety of polymer materials, but not a deposition 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, a roll-to-roll It can be produced in fewer layers by a process, a doctor blading process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage that can be manufactured using the color filter technology of the existing LCD while being easy to realize high resolution and excellent processability. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green) and B (Blue) light emitting parts are mutually planarized, and a stacking method in which 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 therefrom. May also be applied to these WOLEDs.

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, an organic electric device according to an aspect of the present invention is provided.

In one embodiment of the present invention, the present invention comprises a first electrode; Second electrode; One or more organic material layers formed between the first electrode and the second electrode; And an optical efficiency improving layer formed on at least one side of the first electrode and the second electrode opposite to the organic material layer, wherein the optical efficiency improving layer includes a compound represented by the following Formula (1): Provided is an organic electric device characterized by the above-mentioned.

Formula (1)

In the above formula,

X is NAr ² , O or S,

l and o are each independently an integer from 0 to 4,

m and n are each independently an integer from 0 to 3,

R ¹ to R ⁴ are each the same as or different from each other when l, o, m and n are each 2 or more, i) independently of each other deuterium; Tritium; Halogen group; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; And C ₆ ~ C ₃₀ An aryloxy group; or ii) a plurality of R ¹ groups, a plurality of R ² groups, a plurality of R ³ groups or a plurality of R ⁴ groups are bonded to each other to form an aromatic ring Can form (where a group that does not form a ring is as defined in i),

L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ ~ C _{60 divalent} heterocyclic group including at least one hetero atom of O, N, S, Si, and P or including SO ₂ ,

Ar ¹ and Ar ² are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ -C ₃₀ alkoxyl group; And aryloxy group of C ₆ ~ C ₃₀ ; It is selected from the group consisting of,

The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group is deuterium, halogen, silane group, siloxane group, boron group, germanium group , Cyano group, nitro group, -L ¹ -N (R _a ) (R _b ), where L ¹ is a single bond; C ₆ ~ C ₆₀ arylene group; at least one of O, N, S, Si and P C ₂ ~ C _{60 divalent} heterocyclic group containing a hetero atom; Fluorenylene group; C ₃ ~ C ₆₀ Aliphatic ring and C ₆ ~ C ₆₀ Aromatic ring fused ring; C ₁ ~ C _{60 60} alkylene group; C ₂ ~ C ₆₀ Alkenylene group; and C ₂ ~ C ₆₀ Alkylene group; It is selected from the group consisting of R _a and R _b are independently of each other, C ₆ ~ C ₆₀ Aryl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P; C ₁ -C ₅₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₁ - an alkoxy group of C _30; to obtain; and fluorenyl group The selected from the group), coming alkylthio of _{C 1 ~ C 20, C 1} ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of the alkenyl group, C ₂ ~ C ₂₀ alkynyl Weather , C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ substituted with deuterium C ₆ ~ C ₂₀ aryl group, fluorenyl group, C ₂ ~ C ₂₀ containing at least one heteroatom of O, N, S, Si and P It may be further substituted with one or more substituents selected from the group consisting of a heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C ₂₀ arylalkenyl group.

In another embodiment of the present invention, the first electrode is an anode formed of ITO containing Ag, the second electrode is a cathode containing Mg-Ag, the light efficiency improving layer is one side of the second electrode It provides an organic electric element, characterized in that formed on one side opposite to the organic material layer.

In another embodiment of the present invention, the formula (1) may be one of those represented by the following formula (2) to formula (5).

Formula (2) Formula (3)

Formula (4) Formula (5)

In the above formula,

X, R ¹ to R ⁴ , L, Ar ¹ , m, n, o and l are each X, R ¹ to R ⁴ , L, Ar ¹ , m, n, o and l as defined in Formula (1) above. Is the same as

In another embodiment of the present invention, Z in formula (1) may be one of those represented by formula (6) to formula (20).

In another embodiment of the present invention, Y in formula (1) may be one of those represented by formula (21) to formula (32).

In another embodiment of the present invention, the compound represented by Formula (1) may be one of the following compounds.

In another embodiment of the present invention, the present invention is characterized in that the second electrode is a light transmitting cathode electrode, the light efficiency improving layer is formed on one side of the side opposite to the organic material layer of the second electrode Provides an electrical device.

In another embodiment of the present invention, the organic layer is characterized in that the organic material layer is patterned for each of the R, G, B pixels, the light efficiency improvement layer is formed as a common layer for the R, G, B pixels Provided is an element.

In another embodiment of the present invention, the organic material layer is patterned for each of the R, G, B pixels, the light efficiency improvement layer, in the region corresponding to the R pixel for the R, G, B pixels of the organic material layer. And at least one of the formed light efficiency improving layer R, the light efficiency improving layer G formed in the region corresponding to the G pixel, and the light efficiency improving layer B formed in the region corresponding to the B pixel. It provides an organic electric device.

In another embodiment of the present invention, a display device including an organic electric element according to an embodiment of the present invention; And a controller for driving the display device.

The organic electroluminescent device according to an embodiment of the present invention may be at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination.

Hereinafter, the synthesis examples of the chemical formulas according to the present invention and the production examples of the organic electric element will be described in detail by way of examples, but the present invention is not limited to the following examples.

Synthesis Example

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

<Scheme 1>

)(

)

One. Sub  1, Synthesis

Sub 1 of Scheme 1 may be synthesized by the reaction pathways of Scheme 2, Scheme 3 and Scheme 4.

<Scheme 2>

<Scheme 3>

<Scheme 4>

(Scheme 4 is a synthesis method when R ¹ or R ² in the general formula (1) is cyclized)

(One) Sub  Synthesis example of 1-1-1 '

Scheme 5

Sub  1-1-1- 1 'synthetic

Carbazole (50g, 299mmol), 1-iodonaphthalene (91.2g, 358.8mmol), Cu powder (25g, 388.7mmol), 18-crown-6 (7.9g, 29.9mmol), K ₂ CO ₃ (50 g, 358.8 mmol) and DMF (1300 mL) were added thereto, followed by stirring under reflux at 160 ° C. After the reaction was completed, the mixture was extracted with methylene chloride and water, washed with 5% HCl aqueous solution obtained, and brine again. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to give 61.4 g (yield: 70%) of the product.

Sub  1-1-2- 1 'synthetic

Sub 1-1-1-1 '(61.4 g, 209.3 mmol), NBS (59.2 g, 209.3 mmol), BPO (benzoyl peroxide) (2.53 g, 10.5 mmol) and methylene chloride (630 mL) obtained in the above synthesis were rounded. After the bottom flask was stirred at room temperature. After completion of the reaction, the mixture was extracted with methylene chloride and water, and the organic layer was washed again with aqueous NaHCO ₃ solution. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to give 52.2g (yield: 67%) of the product.

Sub  1-1- 1 'synthetic

Sub 1-1-2-1 '(52 g, 140 mmol) and Bis (pinacolato) diboron (42.7 g, 168 mmol), PdCl ₂ (dppf) (3.43 g, 4.2 mmol), KOAc (41.2 g, 420 mmol) obtained in the above synthesis ) And DMF (880 mL) were put into a round bottom flask and stirred under reflux. After the reaction was completed, the resulting organic layer was extracted with ehter, dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give 39.3g (yield: 67%) of the product.

(2) Sub  1-2-5 'Synthesis Example

<Scheme 6>

Sub  1-1-1- 4 'synthetic

Carbazole (50g, 299mmol), iodobenzene (73.2g, 358.8mmol), Cu powder (25g, 388.7mmol), 18-crown-6 (7.9g, 29.9mmol), K ₂ CO ₃ (50 g, 358.8 mmol) and DMF (1300 mL) were added thereto, followed by stirring under reflux at 160 ° C. After completion of the reaction, the mixture was extracted with methylene chloride and water, and the obtained organic layer was washed with 5% aqueous HCl solution and again with brine. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to give 52.4g (yield: 72%) of the product.

Sub  1-1-2- 4 'synthetic

Sub 1-1-1-4 '(52g, 213.7mmol), NBS (60.5g, 213.7mmol), BPO (benzoyl peroxide) (2.6g, 10.7mmol) and methylene chloride (640mL) obtained in the above synthesis After the flask was stirred at room temperature. After the reaction was completed, the mixture was extracted with methylene chloride and water, and the organic layer was washed again with aqueous NaHCO ₃ solution. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to give 46.8 g (yield: 68%) of the product.

Sub  1-1-3-4 'synthesis

Sub 1-1-2-4 '(46.8 g, 145.3 mmol) and quinolin-2-ylboronic acid (26.4 g, 152.6 mmol), Pd ₂ (PPh ₃ ) ₄ (5 g, 4.4 mmol), K ₂ CO ₃ (60.2 g, 435.9 mmol), THF (640 mL) and H ₂ O (320 mL) were placed in a round bottom flask and stirred under reflux. After completion of the reaction, the resulting organic layer was extracted with methylene chloride and water, dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give the product 39.3g (yield: 73%).

Sub  1-2-1-5 'Synthesis

Sub 1-1-3-4 '(39 g, 105.3 mmol), NBS (29.8 g, 105.3 mmol), BPO (benzoyl peroxide) (1.3 g, 5.3 mmol) and methylene chloride (315 mL) obtained in the above synthesis After the reaction, the mixture was stirred at room temperature. After the reaction was completed, the mixture was extracted with methylene chloride and water, and the organic layer was washed again with aqueous NaHCO ₃ solution. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to give 31.2 g (yield: 66%) of the product.

Sub  1-2-5 'Synthesis

Sub 1-2-1-5 '(31 g, 69 mmol) and Bis (pinacolato) diboron (21.0 g, 82.8 mmol), PdCl ₂ (dppf) (1.7 g, 2.1 mmol), KOAc (20.3 g, 207 mmol) and DMF (436 mL) were placed in a round bottom flask and stirred under reflux. After the reaction was completed, the resulting organic layer was extracted with ehter, dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give 23.6g (yield: 69%) of the product.

(3) Sub  1-3-6 'Synthesis Example

Scheme 7

Sub  1-3-1-6 'Synthesis

[1,1'-biphenyl] -4-ylboronic acid (50g, 252.5mmol), 1,4-dibromo-2-nitrobenzene (71.2g, 253.5mmol), Pd (PPh ₃ ) ₄ (8.8g) in a round bottom flask , 7.6 mmol), 2M Na ₂ CO ₃ aqueous solution (382 mL), and toluene (770 mL) were added thereto, and the mixture was stirred at 90 ° C. After the reaction was completed, the mixture was cooled to 20 ° C., diluted with distilled water, and extracted with methylene chloride. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to give 55.5 g (yield: 62%) of the product.

Sub  1-3-2-6 'Synthesis

Sub 1-3-1-6 '(55g, 155.3mmol) and o-dichlorobenzene (496mL) obtained in the above synthesis were dissolved in a round bottom flask, triphenylphosphine (102g, 388.2mmol) was added and stirred under reflux at 200 ° C. . After completion of the reaction, o -dichlorobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 35.5 g (yield: 71%) of the product. )

Sub  1-3-3-6 'synthesis

Sub 1-3-2-6 '(35.5 g, 110.2 mmol) and 2-iodo-4-phenylquinazoline (55 g, 165.3 mmol) obtained from the above synthesis, Cu powder (7.7 g, 121.2 mmol), 18-crown-6 (3 g, 11.2 mmol), K ₂ CO ₃ (22.8 g, 165.3 mmol), and DMF (545 mL) were added thereto, followed by stirring under reflux at 160 ° C. After the reaction was completed, the mixture was extracted with methylene chloride and water, washed with 5% HCl aqueous solution obtained, and brine again. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 40.6 g (yield: 70%) of the product.

Sub  1-3-6 'synthetic

Sub 1-3-3-6 '(40.6 g, 77.1 mmol) and Bis (pinacolato) diboron (21.5 g, 84.8 mmol), PdCl ₂ (dppf) (1.9 g, 2.3 mmol), KOAc (22.7) g, 231.3 mmol) and DMF (485 mL) were added to a round bottom flask and stirred under reflux. After the reaction was completed, the resulting organic layer was extracted with ehter, dried over MgSO ₄ and concentrated, and the resulting organics were purified by silicagel column and recrystallized to give 28.7g (Yield: 65%) of the product Sub 1-3-6 '.

(4) Sub  1-3-7 'Synthesis Example

Scheme 8

Sub  1-3-1-7 'Synthesis

Phenylboronic acid (50g, 410mmol), 1,4-dibromo-2-nitrobenzene (116g, 411.6mmol), Pd (PPh ₃ ) ₄ (14.2g, 12.3mmol), 2M Na ₂ CO ₃ aqueous solution (620mL) ) And toluene (1250 mL) were added to the same method as the synthesis method of Sub 1-3-1-6 ', obtaining 71.8 g (yield: 63%) of product Sub 1-3-1-7'.

Sub  1-3-2-7 'Synthesis

Sub 1-3-1-7 '(71 g, 255.3 mmol), o-dichlorobenzene (816 mL) and PPh ₃ (167.4 g, 638.25 mmol) obtained in the above synthesis method 44 g (yield: 70%) of the product Sub 1-3-2-7 'was obtained by the same method as described above.

Sub  1-3-3-7 'synthesis

Sub 1-3-2-7 '(44 g, 177 mmol) and 3-iododibenzo [b, d] thiophene (82.3 g, 265.5 mmol) obtained in the above synthesis, Cu powder (12.4 g, 194.7 mmol), 18-crown- 6 (4.7g, 17.7mmol), K ₂ CO ₃ (36.7g, 265.5mmol) and DMF (885mL) were carried out in the same manner as the Sub 1-3-3-6 'synthesis method, and the product Sub 1-3- 51.6g (yield: 68%) of 3-7 'was obtained.

Sub  1-3-7 'synthetic

Sub 1-3-3-7 '(51 g, 119 mmol) and Bis (pinacolato) diboron (33.2 g, 130.9 mmol), PdCl ₂ (dppf) (2.9 g, 3.57 mmol), KOAc (35 g, 357 mmol) obtained in the above synthesis ) And DMF (750 mL) were subjected to the same method as the above Sub 1-3-6 'synthesis to obtain 37.3 g (yield: 66%) of product Sub 1-3-7'.

(5) Sub  1-4- 1 'synthetic  example

Scheme 9

Sub  1-4-1-1 'synthesis

Naphthalen-1-ylboronic acid (43.4 g, 252.5 mmol), 1,4-dibromo-2-nitrobenZene (71.2 g, 253.5 mmol), Pd (PPh ₃ ) ₄ (8.8 g, 7.6 mmol), K _{Add 2} CO ₃ (105g, 757.5mmol), THF (1100mL) and H ₂ O (550mL) and proceed in the same manner as the above Sub 1-3-1-6 'synthesis. '53g (yield: 64%) was obtained.

Sub  1-4-2-1 'Synthesis

Sub 1-4-1-1 '(51 g, 155.4 mmol) and o-dichlorobenzene (495 mL) and PPh ₃ (102 g, 388.5 mmol) obtained in the above synthesis were the same as those of the above synthesis method of Sub 1-3-2-6'. Proceed to the method to give 31.3g (yield: 68%) of the product Sub 1-4-2-1 '.

Sub  1-4-3-1 'Synthesis

Sub 1-4-2-1 '(31 g, 105 mmol) and iodobenzene (32.1 g, 157.5 mmol) obtained from the above synthesis, Cu powder (7.3 g, 115.5 mmol), 18-crown-6 (2.8 g, 17.2 mmol) , K ₂ CO ₃ (21.8 g, 157.5 mmol) and DMF (510 mL) were carried out in the same manner as in the above Sub 1-3-3-6 'synthesis to obtain 27 g of the product Sub 1-4-3-1' (yield) : 69%).

Sub  1-4- 1 'synthetic

Sub 1-4-3-1 ′ (27 g, 72.5 mmol) and Bis (pinacolato) diboron (20.3 g, 79.8 mmol), PdCl ₂ (dppf) (1.8 g, 2.2 mmol) and KOAc (21.3 g) obtained in the above synthesis , 217.5 mmol) and DMF (455 mL) were carried out in the same manner as in the Sub 1-3-6 'synthesis, to obtain 20.7 g of a product Sub 1-4-1' (yield: 68%).

(6) Sub  1-4-13 'Synthesis Example

Scheme 10

Sub  1-4-1-13 'Synthesis

Naphthalen-1-ylboronic acid (56.1g, 252.5mmol), 2,4-dibromo-1-nitrobenzene (71.2g, 253.5mmol), Pd (PPh ₃ ) ₄ (8.8g, 7.6mmol), K _{Add 2} CO ₃ (105g, 757.5mmol), THF (1100mL) and H ₂ O (550mL) and proceed to the same experimental method as in the above Sub 1-3-1-6 'synthesis product Sub 1-4-1- 61.1 g (yield: 64%) of 13 'were obtained.

Sub  1-4-2-13 'Synthesis

Sub 1-4-1-13 '(58.8g, 155.4mmol), o-dichlorobenzene (495mL) and PPh ₃ (102g, 388.5mmol) obtained in the above synthesis Proceed in the same manner to give 37.1g (Yield: 69%) of the product Sub 1-4-2-13 '.

Sub  1-4-3-1 'Synthesis

Sub 1-4-2-13 '(36.4 g, 105 mmol) and iodobenzene (32.1 g, 157.5 mmol) obtained from the above synthesis, Cu powder (7.3 g, 115.5 mmol), 18-crown-6 (2.8 g, 17.2 mmol), K ₂ CO ₃ (21.8 g, 157.5 mmol) and DMF (510 mL) were subjected to the same experimental method as in the above Sub 1-3-3-6 'synthesis to obtain the product Sub 1-4-3-1'. 31.5 g (yield: 71%) were obtained.

Sub  1-4-1 'synthesis

Sub 1-4-3-13 '(30.6 g, 72.5 mmol) and Bis (pinacolato) diboron (20.3 g, 79.8 mmol), PdCl ₂ (dppf) (1.8 g, 2.2 mmol), KOAc (21.3) obtained in the above synthesis g, 217.5 mmol) and DMF (455 mL) were subjected to the same experimental method as the above Sub 1-3-6 'synthesis, to obtain 16.4 g of a product Sub 1-4-1' (yield: 66%).

(7) Sub  1-4-15 'Synthesis Example

Scheme 11

Sub  1-4-1-15 'Synthesis

Naphthalen-2-ylboronic acid (70.5g, 410mmol), 2,4-dibromo-1-nitrobenzene (116g, 411.6mmol), Pd (PPh ₃ ) ₄ (14.2g, 12.3mmol), K ₂ CO ₃ (170g, 1230mmol), THF (1800mL) and H ₂ O (900mL) was added and proceeded to the same experimental method as the above Sub 1-3-1-6 'synthesis method to give the product Sub 1-4-1-15'. 87.5 g (yield: 65%) was obtained.

Sub  1-4-2-15 'Synthesis

Sub 1-4-1-15 '(83.8g, 255.3mmol), o-dichlorobenzene (816mL) and PPh ₃ (167.4g, 638.25mmol) obtained in the above synthesis In the same manner as in the experiment to obtain the products Sub 1-4-2-15 '(31.8g) and sub 1-4-2-15'-2 (21.2g), respectively.

Sub  1-4-3-15 'Synthesis

Sub 1-4-2-15 '(31.8g, 107mmol) and 1-iodonaphthalene (40.8g, 160.5mmol) obtained from the above synthesis, Cu powder (7.5g, 117.7mmol), 18-crown-6 (2.8g, 10.7 mmol), K ₂ CO ₃ (22.2 g, 160.5 mmol), and DMF (535 mL) were subjected to the same experimental method as the Sub 1-3-3-6 'synthesis method, and the product Sub 1-4-3-15' 30.3 g (yield 67%) was obtained.

Sub  1-4-15 'synthesis

Sub 1-4-3-15 '(30.3 g, 71.7 mmol), Bis (pinacolato) diboron (20 g, 78.9 mmol), PdCl ₂ (dppf) (1.76 g, 2.2 mmol), KOAc (21.1 g) , 215 mmol) and DMF (450 mL) were subjected to the same experimental method as the above Sub 1-3-6 'synthesis, to obtain 21.9 g (yield: 65%) of product Sub 1-4-15'.

(8) Sub  1-4-16 'Synthesis Example

Scheme 12

Sub  1-4-1-16 'Synthesis

Naphthalen-1-ylboronic acid (62.1 g, 252.5 mmol), 2,4-dibromo-1-nitrobenzene (71.2 g, 253.5 mmol), Pd (PPh ₃ ) ₄ (8.8 g, 7.6 mmol), K _{Add 2} CO ₃ (105g, 757.5mmol), THF (1100mL) and H ₂ O (550mL) and proceed to the same experimental method as in the above Sub 1-3-1-6 'synthesis product Sub 1-4-1- 64 g (yield: 63%) of 16 'was obtained.

Sub  1-4-2-16 'Synthesis

Sub 1-4-1-16 '(62.5g, 155.4mmol), o-dichlorobenzene (495mL), PPh ₃ (102g, 388.5mmol) obtained in the above synthesis Proceed in the same manner to give 38g (yield: 66%) of the product Sub 1-4-2-16 '.

Sub  1-4-3-16 'Synthesis

Sub 1-4-2-16 '(36.4 g, 105 mmol) and 6'-iodo-2,3'-bipyridine (44.4 g, 157.5 mmol) obtained from the above synthesis, Cu powder (7.3 g, 115.5 mmol), 18 -crown-6 (2.8g, 17.2mmol), K ₂ CO ₃ (21.8g, 157.5mmol) and DMF (510mL) were processed by the same experimental method as in the above Sub 1-3-3-6 'synthesis. 38g (yield: 69%) of 1-4-3-16 'were obtained.

Sub  1-4-16 'synthesis

Sub 1-4-3-16 ′ (38 g, 72.5 mmol), Bis (pinacolato) diboron (20.3 g, 79.8 mmol), PdCl ₂ (dppf) (1.8 g, 2.2 mmol), KOAc (21.3 g) obtained in the above synthesis , 217.5 mmol) and DMF (455 mL) were subjected to the same experimental method as the above Sub 1-3-6 'synthesis, to obtain 26.9 g (yield: 65%) of product Sub 1-4-16'.

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

2. Sub  2, synthesis

Sub 2 of Scheme 1 may be synthesized by the intermediate of Synthesis Scheme 2, Scheme 3, Scheme 4 of Sub 1 and the Scheme of Scheme 13 below.

Scheme 13

(One) Sub  2-1-2 'Synthesis Example

Scheme 14

Sub  2-1-1-2 'synthesis

Carbazole (50g, 299mmol), 2-bromo-9- (naphthalen-1-yl) -9H-carbazole (133.6g, 358.8mmol), Cu powder (25g, 388.7mmol), 18 -crown-6 (7.9 g, 29.9 mmol), K ₂ CO ₃ (50 g, 358.8 mmol) and DMF (1300 mL) were added thereto, followed by stirring under reflux at 160 ° C. After completion of the reaction, the mixture was extracted with methylene chloride and water, and the obtained organic layer was washed with 5% aqueous HCl solution and again with brine. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 89.1 g (yield: 65%) of the product Sub 2-1-1-2 '.

Sub  2-1-2 'synthesis

Sub 2-1-1-2 '(89.1 g, 194.3 mmol), NBS (55 g, 194.3 mmol), BPO (benzoyl peroxide) (2.4 g, 9.72 mmol) and methylene chloride (580 mL) obtained in the above synthesis After the flask was stirred at room temperature. After the reaction was completed, the mixture was extracted with methylene chloride and water, and the organic layer was washed again with aqueous NaHCO ₃ solution. Thereafter, the obtained organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give 66.8 g (yield: 64%) of the product Sub 2-1-2 '.

(2) Sub  2-1-3 'Synthesis Example

Scheme 15

Sub  2-1-1-3 'synthesis

Carbazole (50g, 299mmol), 4-iodo-1,1'-biphenyl (100.5g, 358.8mmol), Cu powder (25g, 388.7mmol), 18-crown-6 (7.9g) in round bottom flask , 29.9 mmol), K ₂ CO ₃ (50 g, 358.8 mmol) and DMF (1300 mL) were carried out in the same manner as the Sub 2-1-1-2 'synthesis to yield 65 g (yield: 68%) of the product.

Sub  2-1-3 'synthesis

Sub 2-1-1-3 '(65 g, 203.5 mmol), NBS (57.6 g, 203.5 mmol), BPO (benzoyl peroxide) (2.5 g, 10.2 mmol) and methylene chloride (610 mL) obtained in the above synthesis were obtained. Proceeding in the same manner as in the 2-1-2 'synthesis method, 53.5 g (yield: 66%) of a product was obtained.

(3) Sub  2-1-25 'Synthesis Example

Scheme 16

Sub  2-1-1-25 'synthesis

Naphthalen-1-ylboronic acid (43.4g, 252.5mmol), 1-bromo-2-nitrobenzene (51.2g, 252.5mmol), Pd (PPh ₃ ) ₄ (8.8g, 7.6mmol), K ₂ CO ₃ (105 g, 757.5 mmol), THF (1100 mL) and H ₂ O (550 mL) were added thereto, and the same process as in the above Sub 1-3-1-6 'synthesis was carried out to obtain 41.5 g (yield: 66%) of the product. .

Sub  2-1-2-25 'synthesis

Sub 2-1-1-25 '(41.5g, 166.5mmol), o-dichlorobenzene (530mL) and PPh ₃ (109.3g, 416.3mmol) obtained in the above synthesis Proceed in the same manner to give the product 24.2g (yield: 67%).

Sub  2-1-3-25 'synthesis

Sub 2-1-2-25 '(24.2 g, 111.4 mmol), 2-bromoquinazoline (28 g, 133.7 mmol) obtained in the above synthesis, Cu powder (7.8 g, 122.5 mmol), 18-crown-6 (3 g, 11.1 mmol), K ₂ CO ₃ (23 g, 167 mmol) and DMF (680 mL) were carried out in the same manner as the Sub 2-1-1-2 'synthesis to yield 26.5 g (yield: 69%) of the product.

Sub  2-1- 25 ' synthesis

Sub 2-1-3-25 '(26.5 g, 76.7 mmol), NBS (21.7 g, 76.7 mmol), BPO (benzoyl peroxide) (1 g, 3.8 mmol) and methylene chloride (230 mL) obtained in the above synthesis were obtained. Proceed in the same manner as in the 2-1-2 'synthesis, to obtain 21.8 g (yield: 67%) of the product.

(4) Sub  2-1-26 'Synthesis Example

Scheme 17

Sub  2-1-1 26 ' synthesis

Carbazole (50g, 299mmol), Iodobenzene (73.2g, 358.8mmol), Cu powder (25g, 388.7mmol), 18-crown-6 (7.9g, 29.9mmol), K ₂ CO ₃ (50 g, 358.8 mmol) and DMF (1300 mL) were added thereto, and the procedure was carried out in the same manner as in the Sub 2-1-1-2 'synthesis, to obtain 51.7 g (yield: 71%) of the product.

Sub  2-1-2-26 'synthesis

Sub 2-1-1-26 '(51.7 g, 212.5 mmol), NBS (126.2 g, 446.3 mmol), BPO (benzoyl peroxide) (5.1 g, 21.3 mmol) and methylene chloride (640 mL) obtained in the above synthesis were obtained. The procedure was carried out in the same manner as in the Synthesis of Sub 2-1-2 ', to obtain 58 g (yield: 68%) of the product.

Sub  2-1-26 'synthesis

Sub 2-1-2-26 '(58 g, 145 mmol) obtained from the above synthesis, triphenylen-2-ylboronic acid (39.5 g, 145 mmol), Pd (PPh ₃ ) ₄ (8.8 g, 7.6 mmol), K ₂ CO ₃ (60 g, 435 mmol), THF (640 mL) and H ₂ O (320 mL) were added thereto, and the experiment was carried out in the same manner as in the Sub 1-3-1-6 'synthesis, to obtain 51 g (yield: 64%) of the product.

(5) Sub  2-2-2 'Synthesis Example

Scheme 18

Sub  2-2-2 'synthesis

Sub 1-1-4 "(25g, 67.7mmol), 4,4'-dibromo-1,1'-biphenyl (21.1g, 67.7mmol), Pd (PPh ₃ ) ₄ (2.3) g, ₂ mmol), K ₂ CO ₃ (28.1 g, 203 mmol), THF (300 mL), and H ₂ O (150 mL) were added thereto, and the product was processed in the same manner as in the above Sub 1-3-1-6 'synthesis. g (yield: 67%) was obtained.

(6) Sub  2-2-5 'synthesis example

Scheme 19

Sub  2-2-5 'synthesis

Sub 1-4-13 '(31.8g, 67.7mmol), 4'-bromo-3-iodo-1,1'-biphenyl (24.3g, 67.7mmol), Pd (PPh ₃ ) ₄ (2.3g, 2mmol), K ₂ CO ₃ (28.1g, 203mmol), THF (300mL) and H ₂ O (150mL) was added and proceed to the same experimental method as the above Sub 1-3-1-6 'synthesis method 25.3 g (yield: 65%) of product was obtained.

(6) Sub  2-2-9 'Synthesis Example

Scheme 20

Sub  2-2-5 'synthesis

Dibenzo [b, d] thiophen-2-ylboronic acid (15.4g, 67.7mmol), 3,10-dibromobenzo [f] [1,10] phenanthroline (26.3g, 67.7mmol), Pd as starting materials in round bottom flask (PPh ₃ ) ₄ (2.3 g, ₂ mmol), K ₂ CO ₃ (28.1 g, 203 mmol), THF (300 mL) and H ₂ O (150 mL) were added and the same experiment as the above Sub 1-3-1-6 'synthesis was performed. Proceed to the method to give 22g (yield: 66%) of the product.

(7) Sub  2-2-12 'Synthesis Example

Scheme 21

Sub  2-2-12 'synthesis

Sub 1-1-4 "(25g, 67.7mmol), 3,7-dibromodibenzo [b, d] thiophene 5,5-dioxide (25.3g, 67.7mmol), Pd (PPh ₃ ) ₄ (2.3g, 2mmol), K ₂ CO ₃ (28.1g, 203mmol), THF (300mL) and H ₂ O (150mL) was added and proceed to the same experimental method as the above Sub 1-3-1-6 'synthesis method 23.2 g (yield: 64%) of product was obtained.

(8) Sub  2-3-18 'Synthesis

Scheme 22

Sub  2-3-1-18 'synthesis

(2-ethoxynaphthalen-1-yl) boronic acid (30g, 138.9mmol), 4-bromo-2-fluoro-1-iodobenzene (39.8g, 132.3mmol), Pd (PPh ₃ ) ₄ (4.6g) , 4mmol), K ₂ CO ₃ (55g, 397mmol), THF (580mL) and H ₂ O (290mL) was added to proceed with the same experimental method as the Sub 1-3-1-6 'synthesis method 32g (yield yield) : 70%).

Sub  2-3-2-18 'synthesis

Sub 2-3-1-18 '(32 g, 92.7 mmol) and methylene chloride (270 mL) obtained in the above synthesis were added to a round bottom flask, and cooled to 0 ° C., followed by BBr ₃ (29.1 g, 116 mmol). Was added dropwise. Thereafter, the mixture was stirred at room temperature for 24 hours. When the reaction was completed, the reaction solution was cooled to -78 ° C, methanol and water were added slowly, and the solution was extracted with methylene chloride. The resulting organic layer was dried over MgSO ₄ , concentrated and the resulting organics were purified by silicagel column and recrystallized to give 27.3 g (yield: 93%) of the product.

Sub  2-3-18 'synthetic

Sub 2-3-2-18 '(27.3 g, 86.1 mmol), NMP (N-methyl-2-pyrrolidinone) (370 mL), K ₂ CO ₃ (23.8 g, 172.2 mmol) obtained in the above synthesis in a round bottom flask. After the addition was stirred for 2 hours at 200 ℃. When the reaction was completed, the reaction solution was cooled to room temperature and then diluted with toluene (2.5 L) and extracted with water. The obtained organic layer was dried over MgSO ₄ , concentrated and the resulting organic material was silicagel column and recrystallized to obtain 17g (yield: 66%) of the product.

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

3. Final product ( Final Product ) synthesis

Sub-1 (1.1 equiv), Sub-2 (1 equiv), Pd (PPh ₃ ) ₄ (0.03 equiv), K ₂ CO ₃ (3 equiv), THF (4.4 mL / 1 mmol) and H ₂ 0 (2.2 mL / 1 mmol) was added thereto, followed by stirring under reflux. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain a final product.

P-1 Synthesis Example

Scheme 23

Sub 1-3-1 '(12.2g, 33mmol), Sub 2-3-1' (9.7g, 30mmol), Pd (PPh ₃ ) ₄ (1g, 0.9mmol), K ₂ CO ₃ (12.4g, 90mmol ), THF (132 mL) and H ₂ O (66 mL) were carried out in the same manner as in the final product synthesis to obtain 10.3 g (yield: 71%) of product.

P-9 Synthesis Example

Scheme 24

Sub 1-3-8 '(16g, 33mmol), Sub 2-1-1' (13.1g, 30mmol), Pd (PPh ₃ ) ₄ (1g, 0.9mmol), K ₂ CO ₃ (12.4g, 90mmol) , THF (132 mL) and H ₂ O (66 mL) were processed in the same manner as the final product synthesis method to obtain 14.6 g (yield: 68%) of product.

P-12 Synthesis Example

Scheme 25

Sub 1-1-4 '(12.2g, 33mmol), Sub 2-3-9' (14.3g, 30mmol), Pd (PPh ₃ ) ₄ (1g, 0.9mmol), K ₂ CO ₃ (12.4g, 90mmol ), THF (132 mL) and H ₂ O (66 mL) were carried out in the same manner as the final product synthesis method to obtain 12.7 g (yield: 66%) of the product.

P-29 Synthesis Example

Scheme 26

Sub 1-1-4 '(15.5g, 33mmol), Sub 2-3-14' (13.5g, 30mmol), Pd (PPh ₃ ) ₄ (1g, 0.9mmol), K ₂ CO ₃ (12.4g, 90mmol ), THF (132 mL) and H ₂ O (66 mL) were carried out in the same manner as in the final product synthesis to obtain 13.6 g (yield: 64%) of product.

Of P-32 Synthesis Example

Scheme 27

Sub 1-4-6 '(19g, 33mmol), Sub 2-1-11' (9.4g, 30mmol), Pd (PPh ₃ ) ₄ (1g, 0.9mmol), K ₂ CO ₃ (12.4g, 90mmol) , THF (132 mL) and H ₂ O (66 mL) were processed in the same manner as the final product synthesis method to obtain 13.3 g (yield: 65%) of the product.

P-50 Synthesis Example

Scheme 28

Sub 1-1-4 '(12.2g, 33mmol), Sub 2-4-13' (15.7g, 30mmol), Pd (PPh ₃ ) ₄ (1g, 0.9mmol), K ₂ CO ₃ (12.4g, 90mmol ), THF (132 mL) and H ₂ O (66 mL) were carried out in the same manner as in the final product synthesis to obtain 14.2 g (yield: 69%) of product.

Of P-61 Synthesis Example

Scheme 29

Sub 1-1-9 '(16.4 g, 33 mmol), Sub 2-1-16' (12.7 g, 30 mmol), Pd (PPh ₃ ) ₄ (1 g, 0.9 mmol), K ₂ CO ₃ (12.4 g, 90 mmol), THF (132 mL) and H ₂ O (66 mL) were processed in the same manner as the final product synthesis method to obtain 15.2 g (yield: 71%) of product.

P-64 Synthesis Example

Scheme 30

Sub 1-1-4 '(12.2 g, 33 mmol), Sub 2-1-26' (16.5 g, 30 mmol), Pd (PPh ₃ ) ₄ (1 g, 0.9 mmol), K ₂ CO ₃ (12.4 g, 90 mmol), THF (132 mL) and H ₂ O (66 mL) were processed in the same manner as the final product synthesis method to obtain 13.9 g (yield: 65%) of product.

Of P-77 Synthesis Example

Scheme 31

Sub 1-4-18 '(16.3g, 33mmol), Sub 2-1-29' (14.2g, 30mmol), Pd (PPh ₃ ) ₄ (1g, 0.9mmol), K ₂ CO ₃ (12.4g, 90mmol ), THF (132 mL) and H ₂ O (66 mL) were carried out in the same manner as in the final product synthesis to obtain 14.1 g (yield: 62%) of product.

Of P-99 Synthesis Example

Scheme 32

Sub 1-1-4 '(12.2 g, 33 mmol), Sub 2-2-8' (15.7 g, 30 mmol), Pd (PPh ₃ ) ₄ (1 g, 0.9 mmol), K ₂ CO ₃ (12.4 g, 90 mmol), THF (132 mL) and H ₂ O (66 mL) were processed in the same manner as the final product synthesis method to obtain 14.2 g (yield: 69%) of product.

Of P-100 Synthesis Example

Scheme 33

Sub 1-1-4 '(12.2 g, 33 mmol), Sub 2-2-10' (16.6 g, 30 mmol), Pd (PPh ₃ ) ₄ (1 g, 0.9 mmol), K ₂ CO ₃ (12.4 g, 90 mmol), THF (132 mL) and H ₂ O (66 mL) were processed in the same manner as the final product synthesis method to obtain 14.4 g (yield: 67%) of product.

Of P-103 Synthesis Example

Scheme 34

Sub 1-1-4 '(12.2 g, 33 mmol), Sub 2-2-13' (17.6 g, 30 mmol), Pd (PPh ₃ ) ₄ (1 g, 0.9 mmol), K ₂ CO ₃ (12.4 g, 90 mmol), THF (132 mL) and H ₂ O (66 mL) were processed in the same manner as the final product synthesis method to obtain 14.8 g (yield: 66%) of product.

On the other hand, FD-MS values of the compounds P-1 ~ P-103 of the present invention prepared according to the synthesis examples as described above are shown in Table 3.

Manufacturing Evaluation of Organic Electrical Device

The compound of the present invention is a light efficiency improving layer formed on a Mg-Ag second electrode (cathode) of a device including a pair of electrodes of a first electrode (anode) and a second electrode (cathode). A manufacturing example for the organic electric element will be described.

However, as a light-efficiency capping layer used after the Mg-Ag cathode in a device including a pair of electrodes of the first electrode (anode) and the second electrode (cathode), the compound described in the formula (1) is included. Since only a large number of organic electric devices are used, only some of the organic electric devices including the compound described in Formula (1) in the light efficiency improving layer will be described.

[ Example  I] Red Organic Electrical Element

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm as a hole transport compound on the film to form a hole transport layer. Formed. Thereafter, CBP [4,4'-N, N'-dicarbazole-biphenyl] is used as a host on the hole transport layer, and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate as a dopant. ] Was deposited to a weight of 95: 5 to deposit a 30 nm thick light emitting layer. Then, (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a hole blocking layer to a thickness of 10 nm. An electron injection layer was formed on the hole blocking layer with a thickness of 40 nm of tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ). Subsequently, LiF, an alkali metal halide, is deposited to a thickness of 0.2 nm, and then Mg-Ag is deposited to a thickness of 12 nm to deposit a cathode, and then a compound of the present invention (compound p-) is formed to a thickness of 60 nm on the cathode. One of 1 to P-103) was formed as a light efficiency capping layer to fabricate an organic electric device.

[ Example  Ⅱ] Green Organic Electrical Device

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ^1- A phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a hole injection layer having a thickness of 60 nm. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. . 95: 5 weight of CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] as a dopant on the hole transport layer. A light emitting layer having a thickness of 30 nm was deposited by doping. After that, vacuum (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuumed to a hole blocking layer on the light emitting layer at a thickness of 10 nm. A tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was deposited to a thickness of 40 nm with an electron injection layer. Subsequently, LiF, an alkali metal halide, is deposited to a thickness of 0.2 nm, and then Mg-Ag is deposited to a thickness of 12 nm to deposit a cathode, and then a compound of the present invention (compound p-) is formed to a thickness of 60 nm on the cathode. One of 1 to P-103) was formed as a light efficiency capping layer to fabricate an organic electric device.

[ Example  Ⅲ] Blue Organic Electrical Element

First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ^1- A phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a hole injection layer having a thickness of 60 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited on the hole injection layer to a thickness of 60 nm. A hole transport layer was formed. Thereafter, a light emitting layer having a thickness of 30 nm was deposited by doping 9,10-di (naphthalen-2-yl) anthracene as a host and BD-052X (Idemitsukosan) as a dopant at a weight of 93: 7 on the hole transport layer. Then, vacuum (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (abbreviated as BAlq) was vacuumed to a thickness of 10 nm as a hole blocking layer on the light emitting layer. A tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq3) was deposited to a thickness of 40 nm with an electron transport layer. Subsequently, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then a Mg-Ag was deposited to a thickness of 12 nm to deposit a cathode, and then the compound of the present invention to a thickness of 60 nm on the cathode. An organic electric device was fabricated by forming a film (one of the compounds p-1 to P-103) into a capping layer.

[ Comparative example  One] Red Organic Electrical Element

An organic electric device was manufactured in the same manner as in [Example I], except that Alq ₃ was used instead of the compound of the present invention as the light efficiency improving layer material.

[ Comparative example  2] Green Organic Electrical Element

An organic electric device was manufactured in the same manner as in [Example II], except that Alq ₃ was used instead of the compound of the present invention as a light efficiency improving layer material.

[ Comparative example  3] Blue Organic Electrical Element

An organic electric device was manufactured in the same manner as in [Example III], except that Alq ₃ was used instead of the compound of the present invention as the light efficiency improving layer material.

[ Comparative example  4] Red Organic Electrical Element

An organic electric device was manufactured in the same manner as in [Example I], except that no light efficiency improving layer was used.

[ Comparative example  5]  Green Organic Electrical Element

An organic electric device was manufactured in the same manner as in [Example II], except that a light efficiency improving layer was not used.

[ Comparative example  6] Blue Organic Electrical Element

An organic electric device was manufactured in the same manner as in [Example III], except that a light efficiency improving layer was not used.

Thus prepared [Example I] (Experimental Example (1) to Experimental Example (102)), [Example II] (Experimental Example (103) to Experimental Example (144)), [Experimental Example III] (Experimental Example (145) to Experimental Example (170)), Comparative Example 1 to Comparative Example 6 was subjected to a forward bias DC voltage to the organic electrical device was measured for electroluminescence (EL) characteristics by the PR-650 of photoresearch, Measurement result The T95 life was measured using a life-time measuring instrument manufactured by McScience Inc. at 2500 cd / m ² reference luminance.

Table 4 shows the device fabrication and evaluation results of [Example I] (Experimental Example (1) to Experimental Example 102), Comparative Example 1 and Comparative Example 4 to which the compound according to the present invention was applied, and Table 5 Shows the device fabrication and evaluation results of [Example II] (Experimental Example (103) to Experimental Example (144)), Comparative Example 2 and Comparative Example 5 to which the compound according to the present invention was applied. And, Table 6 shows the device fabrication and the evaluation results of the [Experimental Example III] (Experimental Example (145) to Experimental Example 170), Comparative Example 3 and Comparative Example 6 to which the compound according to the present invention is applied.

As can be seen from the results of Tables 4 to 6, the organic electric device using the material for the organic electric device of the present invention as a light efficiency improving layer can be markedly improved in high color purity and luminous efficiency. Comparing the results of devices with and without a light efficiency improving layer, it can be seen that the color purity and efficiency of the device including the light efficiency improving layer are increased, and Alq is used as the light efficiency improving layer. _When using the compound of the present invention than when using ₃ , it can be seen that the color purity and efficiency is significantly improved. This can be explained by the refractive index, it is obvious that the organic electric device using the compound of the present invention having a refractive index of 1.8 to 2.0 than Alq ₃ having a refractive index of 1.5 to 1.6 has a high efficiency.

Even if the compounds of the present invention are used in other organic material layers of the organic electric device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer and a hole injection layer, it is obvious that the same effect can be obtained.

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

101, 201: substrate 102, 202: first electrode
103, 203: hole injection layer 104, 204: hole transport layer
105, 205: light emitting layer 106, 206: electron transport layer
107 and 207 electron injection layer 108 and 208 second electrode
109, 209: light efficiency improving layer

Claims (12)

A first electrode; Second electrode; One or more organic material layers formed between the first electrode and the second electrode; And an optical efficiency improvement layer formed on at least one side of the first electrode and the second electrode opposite to the organic material layer.
The optical efficiency improving layer is an organic electroluminescent device comprising a compound represented by the following formula (1):
<Formula 1>

In Chemical Formula 1,
X is N (Ar ² ), O or S,
l and o are each independently an integer from 0 to 4,
m and n are each independently an integer from 0 to 3,
R ¹ to R ⁴ are each the same as or different from each other when l, o, m and n are each 2 or more, i) independently of each other deuterium; Tritium; Halogen group; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; And C ₆ ~ C ₃₀ An aryloxy group; or ii) a plurality of R ¹ groups, a plurality of R ² groups, a plurality of R ³ groups or a plurality of R ⁴ groups are bonded to each other to form an aromatic ring Can form (where a group that does not form a ring is as defined in i),
L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Divalent fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And a C ₂ ~ C _{60 divalent} heterocyclic group including at least one heteroatom of O, N, S, Si, and P;
Ar ¹ and Ar ² are each independently a C ₆ ~ C ₆₀ aryl group; Fluorenyl groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ -C ₃₀ alkoxyl group; And aryloxy group of C ₆ ~ C ₃₀ ; It is selected from the group consisting of,
The aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group is deuterium, halogen, silane group, siloxane group, boron group, germanium group , a cyano group, an alkyne of the nitro group, C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the C ₂ -C containing at least one heteroatom of a diary, a C ₆ -C ₂₀ aryl group, a C ₆ -C ₂₀ aryl group substituted with deuterium, a fluorenyl group, O, N, S, Si, and P It may be further substituted with one or more substituents selected from the group consisting of ₂₀ heterocyclic groups, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C ₂₀ arylalkenyl group. The method of claim 1,
The first electrode is an anode formed of ITO containing Ag, the second electrode is a cathode containing Mg-Ag,
The optical efficiency improving layer is formed on one side of the second electrode opposite to the organic material layer, characterized in that the organic electric element. The method of claim 1,
Formula 1 is an organic electric device, characterized in that represented by one of the following formula (2):
<Formula 2><Formula3>

<Formula 4><Formula5>

In Chemical Formulas 2 to 5, X, R ¹ to R ⁴ , L, Ar ¹ , m, n, o and l are the same as defined in claim 1. The method of claim 1,
Z in Chemical Formula 1 is one of the following Chemical Formulas 6 to 20:

. The method of claim 1,
Y in Formula 1 is an organic electric device, characterized in that one of the following formula 21 to formula 32:

. The method of claim 1,
The compound represented by Chemical Formula 1 is one of the following compounds:

. The method of claim 2,
And the second electrode is a light transmissive cathode electrode, and the light efficiency improving layer is formed on one side of the second electrode opposite to the organic material layer. The method of claim 1,
The organic material layer is patterned for each of R, G, and B pixels, and the light efficiency improving layer is formed as a common layer for the R, G, and B pixels. The method of claim 1,
The organic layer is patterned for each of R, G, and B pixels,
The light efficiency improving layer may include a light efficiency improving layer R formed in a region corresponding to an R pixel for the R, G, and B pixels of the organic material layer, a light efficiency improving layer G formed in a region corresponding to the G pixel, And at least one of a light efficiency improving layer (B) formed in a region corresponding to the B pixel. The method of claim 1,
The organic material layer is at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer and an electron injection layer. A display device comprising the organic electroluminescent element of claim 1; And
And a controller for driving the display device. The method of claim 11,
The organic electronic device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochrome or white illumination device.

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