KR20180128292A - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

Disclosed are a compound represented by chemical formula 1, an organic electric device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, and an electronic device including the same. By including the compound represented by the chemical formula 1 in the organic material layer, the driving voltage of the organic electric device can be lowered, and the luminous efficiency and lifespan can be improved.

Description

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

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 is often formed of a multilayer 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.

The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as a light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

Currently, the portable display market is growing in size as a large-area display, which requires more power than the power consumption required by existing portable displays. Therefore, power consumption becomes a very important factor for portable displays, which have a limited power source, such as a battery, and efficiency and lifetime issues must be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases. As the driving voltage decreases, the crystallization of the organic material due to Joule heating, which occurs during driving, And the lifetime tends to increase. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimum combination of the energy level and the T ₁ value between the respective organic layers, and the intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long life and high efficiency can be achieved at the same time. Therefore, it is necessary to develop a light emitting material having high thermal stability and achieving a charge balance in the light emitting layer efficiently.

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 and an electron injecting material is supported by a stable and efficient material However, the development of stable and efficient organic material layer materials for organic electroluminescent devices has not been sufficiently developed yet. Therefore, development of new materials is continuously required, and development of a host material for a light emitting layer is urgently required.

An object of the present invention is to provide a compound capable of lowering the driving voltage of a device and improving the luminous efficiency, color purity and lifetime of the device, an organic electric device using the same, and an electronic device therefor.

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 embodiment of the present invention, not only the driving voltage of the device can be lowered, but also the luminous efficiency, color purity and lifetime of the device can be greatly improved.

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

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference 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, the terms first, second, A, B, (a), (b), and the like can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the present specification, the 'group name' corresponding to the aryl group, the arylene group, the heterocyclic group and the like exemplified as the examples of the respective symbols and substituents thereof may be described as 'the name of the group reflecting the singer' You may. For example, in the case of phenanthrene, which is a kind of aryl group, a monovalent 'group' may be named 'phenanthryl' and a bivalent group may be named 'phenanthrylene' It may be described as "phenanthrene" which is the name of the parent compound. Similarly, in the case of pyrimidine, it may also be described as 'pyrimidine' irrespective of the valence number, or may be described as the 'name of the group' of the corresponding singer, such as pyrimidine di have.

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, the substituent R ¹ is absent. That is, when a is 0, it means that all of the carbons forming the benzene ring are bonded to hydrogen. In this case, And the chemical formula or compound may be described. 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, for example, , R < ¹ > may be the same or different from each other when a is an integer of 2 or more.

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

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

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

Also, although not shown, the organic electroluminescent device according to an embodiment of the present invention further includes a protective layer or a light-efficiency-improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer can do.

The compound according to one embodiment of the present invention applied to the organic layer includes a hole injecting layer 130, a hole transporting layer 140, a light emitting auxiliary layer 151, an electron transporting auxiliary layer, an electron transporting layer 160, 170), a host or a dopant material of the light emitting layer 150, or a material of the light efficiency improving layer. For example, the compound of the present invention can be used as a material for the light emitting layer 150, the hole transporting layer 140, and / or the light emitting auxiliary layer 151, and can be preferably used as a host material for the light emitting layer 150.

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

Accordingly, in the present invention, by forming the light emitting layer 150 using the compound represented by Chemical Formula 1, the energy level and T ₁ value between each organic material layer, the intrinsic characteristics (mobility, interface characteristics, etc.) It is possible to simultaneously improve the life span and the efficiency.

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

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

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

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

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

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

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

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

 ≪ Formula 1 >

Each symbol in the above formula is defined as follows.

Z ¹ to Z ⁸ are independently of each other C (R ₀ ) or N;

Wherein R < ₀ > is independently selected from the group consisting of 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 fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); and adjacent R ₀ may be bonded to each other to form a ring.

When R ₀ is an aryl group, it may preferably be an aryl group of C ₆ to C ₃₀ , more preferably a C ₆ to C ₁₈ aryl group, specifically, phenyl, naphthyl, biphenyl, terphenyl, and the like. When R ₀ is a heterocyclic group, preferably a C ₂ to C ₃₆ heterocyclic group, specifically a carbazole, a dibenzofuran, a spirochromenoindolefluorene, a phenyl spirochromenoindol cyclopentadiene, Phenylspirochromenoindolecyclopentadipyridine, triphenyldihydroindolocarbazole, and the like. When R ₀ is a fluorenyl group, it may be 9,9-dimethyl-9H-fluorene.

X ¹ and X ² are independently of each other a single bond, N (R '), O or S.

R 'is hydrogen; A C ₁ to C ₅₀ alkyl group; A C ₆ to C ₆₀ aryl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b );

When R 'is an aryl group, preferably an aryl group of C ₆ to C ₃₀ , more preferably a C ₆ to C ₁₈ aryl group, specifically phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, fluororan Tungsten, triphenylene, pyrene, and the like. When R 'is a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₈ heterocyclic group, specifically pyridine, pyrimidine, triazine, indole, Indolopyrimidine, indolopyrimidine, quinoxaline, benzoquinazoline, pyridoquinazoline, carbazole, indolocarbazole, dibenzofuran, benzonaphthofuran, benzothienopyridine, benzothienopyrimidine, benzofuro Pyrimidine, dimethylbenzoindenopyrimidine, pyridopyrrolocarbazole, and the like. R 'is a fluorene group in the case, 9,9-dimethyl--9H- fluorene, 9,9-diphenyl -9 H - fluorene group, a 9,9'-bi-Spy fluorene, benzo fluorene spy Spiro [benzo [b] fluorene-11,9'-fluorene), and the like.

Ar ¹ and Ar ² are each independently 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 fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); Ar ¹ and Ar ² may combine with each other to form a ring. The ring formed by bonding Ar ¹ and Ar ² to each other may be fluorene, and when they are bonded to each other, a compound can be formed as a spy.

L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A 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 C ₂ to C ₆₀ heterocyclic group.

R _a and R _b are each independently a C ₆ to C ₆₀ aryl group; A fluorenyl group; A 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 C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P;

Wherein R _0, R ', Ar ^1, Ar ^2, L', R _a and R _b is one bonded to each other adjacent R ₀ together a ring, formed by the Ar ¹ and Ar ² formed by combining each other ring are each deuterium ; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; Aryl alkenyl group of C ₈ -C _20; A C ₆ -C ₃₀ aryloxy group; And a combination of these.

Preferably, the formula (1) may be represented by one of the following formulas (2) to (10).

&Lt; Formula 2 > < EMI ID =

&Lt; Formula 5 > < EMI ID =

&Lt; Formula 8 > < EMI ID =

In the formulas (2) to (10), each symbol can be defined as follows.

Ar ¹ , Ar ² , Z ¹ to Z ⁸ are as defined in the formula (1).

L ¹ and L ² independently of one another are a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A 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 C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P;

Ar ⁴ and Ar ⁵ are each independently 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 fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); L ', R _a and R _b are as defined in formula (1).

In the above formula (1), R 'may be represented by one of the following formulas (A-1) to (A-5).

<Formula A-1> <Formula A-2> <Formula A-3>

&Lt; Formula (A-4) <A-5>

In the above formulas (A-1) to (A-5), each symbol may be defined as follows.

L is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A 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 C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P;

At least one of X ¹ to X ²² is N, and the others are C (R ¹ ).

R &lt; ¹ &gt; is hydrogen; heavy hydrogen; halogen; A C ₆ to C ₂₀ aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one hetero atom in the P C _20; 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 ₁ to C ₂₀ alkoxyl group; And an aryloxy group of C ₆ to C ₃₀ ; and adjacent R ^{1 s} may bond to each other to form a ring.

Ar ⁶ is a C ₆ to C ₂₀ aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one hetero atom in the P C _20; 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 ₁ to C ₂₀ alkoxyl group; And an aryloxy group having from ₆ to ₃₀ carbon atoms.

F ¹ and F ² is independently N (R ¹ ), S, O or C (R ¹ ) (R ² ), a and b are each an integer of 0 or 1, and a + b is an integer of 1 or more.

R ¹ and R ² are independently of each other hydrogen; An alkyl group having ₁ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; And a C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from the group consisting of O, N, S, Si and P, and R ¹ and R ² are bonded to each other to form a spiro compound can do.

Specifically, Formula 1 may be one of the following compounds.

In another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and an organic material layer disposed between the first electrode and the second electrode.

The organic material layer is at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, and a light emitting layer, and the organic material layer may include at least one of the compounds. That is, the organic material layer may include one or more compounds represented by Formula 1, and the compound represented by Formula 1 may be used as a host material for the light emitting layer.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

Synthetic example

The final products represented by Formula 1 according to the present invention may be synthesized by reacting Core 1 or Core 2 with Sub 1 as shown in Reaction Scheme 1 or Reaction Scheme 2, but the present invention is not limited thereto.

<Reaction Scheme 1>

In the above Reaction Scheme 1, Hal ¹ is I or Br or Cl.

<Reaction Scheme 2>

In the above Reaction Scheme 2, Hal ¹ is I or Br or Cl.

Ⅰ. Synthesis of Core

Core 1 of Reaction Scheme 1 and Core 2 of Reaction Scheme 2 may be synthesized as follows but are not limited thereto.

1. Core 1-1 Synthetic example

(1) Core 1-I-1 synthesis

3-chlorocoumairn (150.0 g, 830.6 mmol) were placed in a round bottom flask, 2-chloroaniline (169. 54 g , 1,329.0 mmol) and _{Pd 2 (dba) 3 (22.82} g, 24.9 mmol) and P (t-Bu) ₃ (32.4 ml, 66.4 mmol) and NaOt-Bu (239.49 g, 2,491.8 mmol) were dissolved in toluene (4,000 mL) and stirred at 110 ° C. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 146.69 g (yield: 65% .

 (2) Core 1-I-I-1 synthesis

Into the Core 1-I-1 (146.69 g, 539.9 mmol) obtained in the above synthesis in a round bottom _{flask, Pd (OAc) 2 (2.42} g, 10.8 mmol) and _{P (t-Bu) 3 ·} HBF 4 (15.66 g , 54.0 mmol), and K ₂ CO ₃ (223.86 g, 1,619.7 mmol) were placed in a 250 mL _three- necked flask, and the mixture was heated to 150 ° C. with dimethylformamide (2,500 mL). After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 91.44 g (yield: 72%) of the product.

 (3) Core 1-I-I-I-1 synthesis

After dissolving 2-bromo-1,1'-biphenyl (135.92 g, 583.1 mmol) in THF (3,000 mL), the reaction temperature was lowered to -78 ° C and n-BuLi (57.48 mL, 2.5 M in hexane) After slow dropwise addition, the reaction was stirred for 1 hour. Core 1-II-1 (91.44 g, 388.7 mmol) obtained in the above synthesis was dissolved in THF, and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, water was added to the reaction mixture to quench the reaction mixture. The reaction mixture was filtered to remove water, and the organic layer was dried over MgSO ₄ and concentrated to obtain 119.59 g of the product (yield: 79%).

(4) Core 1-1 synthesis

Core 1-III-1 (119.59 g, 307.1 mmol) obtained in the above synthesis was placed in a round bottom flask and dissolved in acetic acid (1,300 mL). A few drops of HCl were slowly added and stirred at 80 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was neutralized with aqueous Na ₂ SO ₄ solution 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 94.67 g (yield: 83% .

2. Core 1-2 Synthetic example

(1) Core 1-I-2 synthesis

3-chlorocoumairn (150.0 g, 830.6 mmol) were placed in a round bottom flask, 2-chloroaniline (169. 54 g , 1,329.0 mmol) and _{Pd 2 (dba) 3 (22.82} g, 24.9 mmol) and P (t-Bu) ₃ (32.4 ml, 66.4 mmol) and NaOt-Bu (239.49 g, 2,491.8 mmol) were dissolved in toluene (4,000 mL) and stirred at 110 ° C. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 151.20 g (yield: 67% .

 (2) Core 1-I-I-2 synthesis

Into the Core 1-I-2 (151.20 g, 556.5 mmol) obtained in the above synthesis in a round bottom _{flask, Pd (OAc) 2 (2.50} g, 11.1 mmol) and _{P (t-Bu) 3 ·} HBF 4 (16.15 g , 55.6 mmol), K ₂ CO ₃ (230.74 g, 1,669.5 mmol), and the mixture was heated to 150 ° C. with dimethylformamide (2,700 mL), and the reaction mixture was stirred for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 92.95 g (yield: 71%) of the product.

(3) Core 1-I-I-I-2 and core side 1-2 synthesis

Core side 1-I-2 composite

3-Bromopyridine (130 g, 822.8 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) g, 987.3 mmol), PdCl ₂ (dppf) (20.16 g, 24.7 mmol) and potassium acetate (242.24 g, 2,468.4 mmol) were placed in a round bottom flask and Toluene (4,000 mL) was added and stirred at 100 ° C for 3 hours. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. After filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 160.28 g of the product (yield: 95%).

Core side 1-2 synthesis

Core side 1-I-2 ( 160.28 g, 160.28 mmol) obtained in the synthesis, 1,2-dibromobenzene (219.23 g, 1,563.2 mmol), Pd (PPh 3) 4 (27.10 g, 23.4 mmol) and sodium hydroxide (93.79 g, 2,344.9 mmol) were placed in a round bottom flask, and THF (3,900 mL) and H ₂ O (1,500 mL) were heated to 80 ° C and stirred for 6 hours. After the reaction was completed, H ₂ O was removed and the organic layer was concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 146.38 g (yield: 80%) of the product.

Core 1-I-I-I-2 synthesis

Core side 1-2 (138.75 g, 592.7 mmol), which is one of the materials obtained in the above synthesis, was dissolved in THF (3,000 mL), the temperature of the reaction was lowered to -78 ° C and n-BuLi (58.44 mL, hexane) was slowly added dropwise and the reaction was stirred for 1 hour. Core 1-II-2 (92.95 g, 395.1 mmol) obtained in the above synthesis was dissolved in THF, injected into the reaction solution, and stirred at room temperature for 4 hours. After completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction mixture was removed. After the filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 128.05 g of the product (yield: 83%).

(4) Core 1-2 synthesis

Core 1-III-2 (128.05 g, 328.0 mmol) obtained in the above synthesis was placed in a round bottom flask and dissolved in acetic acid (1,600 mL). A few drops of HCl were slowly added and stirred at 80 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was neutralized with an aqueous solution of Na ₂ SO ₄ 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 106.26 g (yield: 87% .

3. Core 1-3 Synthetic example

(1) Core 1-I-3 synthesis

2-chloro-2H-pyrano [3,2-c] pyridin-2-one (150.0 g, 828.8 mmol) was added to a round- bottomed flask and 2-chloroaniline (169.54 g, 1,326.0 mmol) and Pd _{2 ) 3 (22.77 g, 24.9 mmol} ) and _{P (t-Bu) 3 (} 32.3 ml, 66.3 mmol) and into the NaOt-Bu (238.96 g, 2,486.3 mmol), was dissolved in toluene (4,000 mL), at 110 ℃ Lt; / RTI &gt; After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 153.68 g of the product (yield: 68% .

(2) Core 1-I-I-3 synthesis

Pd (OAc) ₂ (2.53 g, 11.3 mmol) and P (t-Bu) ₃ -HBF4 (16.35 g, 11.3 mmol) were added to a round bottom flask, 56.3 mmol), K ₂ CO ₃ (233.67 g, 1,690.7 mmol), and the mixture was heated to 150 ° C. with dimethylformamide (2,500 mL), and the reaction mixture was stirred for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 99.85 g (yield: 75%) of the product.

(3) Core 1-I-I-I-3 synthesis

After dissolving 2-bromo-biphenyl (147.18 g, 631.4 mmol) in THF (3,000 mL), the temperature of the reaction was lowered to -78 ° C and n-BuLi (62.25 mL, 2.5 M in hexane) Was stirred for 1 hour. Core 1-II-3 (99.85 g, 422.7 mmol) obtained in the above synthesis was dissolved in THF, and the mixture was stirred at room temperature for 4 hours. After the reaction was completed, water was added to the reaction mixture to quench water. The water in the reaction mixture was removed, and the organic layer was dried over MgSO ₄ and concentrated to obtain 138.63 g of the product (yield: 84%).

(4) Core 1-3 synthesis

Core 1-III-3 (390.44 g, 328.0 mmol) obtained in the above synthesis was placed in a round bottom flask and dissolved in acetic acid (1,300 mL). A few drops of HCl were slowly added and stirred at 80 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was neutralized with an aqueous Na ₂ SO ₄ solution 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 105.04 g (yield: 86% .

4. Core 1-4 Synthetic example

(1) Core 1-I-4 synthesis

3-chlorocoumarin (150.0 g, 830.6 mmol) were placed in a round bottom flask, 3-chloropyridine-4-amine (170.85 g, 1,329.0 mmol) and _{Pd 2 (dba) 3 (22.82} g, 24.9 mmol) and P (t- Bu) ₃ (32.4 ml, 66.4 mmol) and NaOt-Bu (239.49 g, 2,491.8 mmol) were put in toluene (4,000 mL) and stirred at 110 ° C. After completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction product was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 149.49 g (yield: 66% .

(2) Core 1-I-I-4 synthesis

Pd (OAc) ₂ (2.46 g, 11.0 mmol) and P (t-Bu) _3. HBF ₄ (15.91 g, 11.0 mmol) were added to a round bottom flask. , 54.8 mmol) and K ₂ CO ₃ (227.30 g, 1,644.6 mmol) were added and the mixture was heated to 150 ° C. with dimethylformamide (2,500 mL). The reaction mixture was stirred for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 90.65 g (yield: 70%) of the product.

(3) Core 1-I-I-I-4 synthesis

After dissolving 2-bromo-biphenyl (134.18 g, 575.6 mmol) in THF (3,000 mL), the reaction temperature was lowered to -78 ° C and n-BuLi (56.75 mL, 2.5 M in hexane) Was stirred for 1 hour. Core 1-II-4 (90.65 g, 383.7 mmol) obtained in the above synthesis was dissolved in THF, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction mixture was removed. After the filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 127.35 g of the product (yield: 85%).

(4) Core 1-4 synthesis

Core 1-III-4 (127.35 g, 326.2 mmol) obtained in the above synthesis was placed in a round bottom flask and dissolved in acetic acid (1,200 mL). A few drops of HCl were slowly added and stirred at 80 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was neutralized with an aqueous Na ₂ SO ₄ solution 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 106.90 g (yield: 88% .

5. Core 1-10 Synthetic example

(1) Core 1-I-10 synthesis

3-chloro-2H-thiopyrano [ 3,2-c] pyridin-2-one (150.0 g, 759.0 mmol) were placed in a round bottom flask, 3-chloropyridin-4-amine (156.11 g, 1,214.3 mmol) and Pd ₂ (dba) ₃ (20.85 g, 22.8 mmol), P (t-Bu) ₃ (29.6 ml, 60.7 mmol) and NaOt-Bu (218.83 g, 2,276.9 mmol) were dissolved in toluene (4,000 mL) Lt; 0 &gt; C. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 158.33 g (yield: 72% .

(2) Core 1-I-I-10 synthesis

Placed in the Core 1-I-10 (163.31 g, 563.6 mmol) obtained in the above Synthesis round bottom _{flask, Pd (OAc) 2 (2.53} g, 11.3 mmol) and _{P (t-Bu) 3 ·} HBF 4 (16.35 g , 56.4 mmol) and K ₂ CO ₃ (233.70 g, 1,690.9 mmol) were added and the mixture was heated to 150 ° C. with dimethylformamide (2,800 mL), and the reaction mixture was stirred for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 101.36 g (yield: 71%) of the product.

(3) Core 1-I-I-I-10 and core side 1-10 synthesis

Core side 1-I-10 composite

3-Bromopyridine (200 g, 1,265.8 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) g, 1,519.0 mmol) and _{PdCl 2 (dppf) (31.01 g} , 38.0 mmol) and a potassium acetate (372.68 g, 3,797.5 mmol ) into a round bottom flask was put in Toluene (6,000 mL) was stirred for 3 hours in 100 ℃. After completion of the reaction, the reaction product was quenched with water, and the water in the reaction product was removed. After filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 220.63 g (yield: 85%) of the product.

Core side 1-10 synthesis

Pd (PPh ₃ ) ₄ (37.30 g, 32.3 mmol) and sodium hydroxide were added to a solution of Core side 1-I-10 (220.63 g, 1,075.9 mmol), 4-bromo-3-iodopyridine (610.89 g, by heating (129.11 g, 3,227.8 mmol) into a round bottom flask, THF (5,300 mL) and _{H 2 O (2,500 mL) 80} ℃ together, and the mixture was stirred for 6 hours. After the reaction was completed, H ₂ O was removed and the organic layer was concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 154.29 g (yield: 61%) of the product.

Core 1-I-I-I-10 synthesis

Core side 1-10 (141.11 g, 600.3 mmol) obtained in the above synthesis was dissolved in THF (3,000 mL), the temperature of the reaction was lowered to -78 ° C, and n-BuLi (59.19 mL, 2.5 M in hexane) After the dropwise addition, the reaction was stirred for 1 hour. Core 1-II-10 (101.36 g, 400.2 mmol) obtained in the above synthesis was dissolved in THF, injected into the reaction solution, and stirred at room temperature for 4 hours. After the completion of the reaction, water was added to the reaction mixture to quench the reaction mixture, and water in the reaction mixture was removed. After filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 127.82 g of the product (yield: 78%).

(4) Core 1-10 synthesis

Core 1-III-10 (127.82 g, 312.2 mmol) obtained in the above synthesis was placed in a round bottom flask and dissolved in acetic acid (1,500 mL). A few drops of HCl were slowly added and stirred at 80 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was neutralized with an aqueous Na ₂ SO ₄ solution 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 114.86 g (yield: 94% .

6. Core 2-5 Synthetic example

(1) Core 2-I-5 synthesis

Furo [3,2-c] pyridine-2-carboxylic acid (150.0 g, 919.5 mmol) was placed in a round bottom flask and dissolved in CH ₂ Cl ₂ (1,800 mL) and stirred at 70 ° C. SOCl ₂ (160.80 g, 1,351.7 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 156.95 g (yield: 94% .

(2) Core 2-I-I-5 synthesis

Core 2-I-5 (156.95 g, 864.4 mmol) obtained in the above synthesis was placed in a round bottom flask and 3-chloropyridin-4-amine (177.79 g, 1,383.0 mmol) and Pd ₂ (dba) ₃ put mmol) and _{P (t-Bu) 3 (} 13.99 ml, 69.1 mmol) and NaOt-Bu (249.56 g, 2,593.1 mmol), was dissolved in toluene (4,000 mL), and stirred at 110 ℃. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 151.40 g (yield: 64% .

(3) Core 2-I-I-I-5 synthesis

Placed in the Core 2-II-5 (151.40 g, 553.2 mmol) obtained in the above Synthesis round bottom _{flask, Pd (OAc) 2 (2.48} g, 11.1 mmol) and _{P (t-Bu) 3 ·} HBF 4 (16.05 g , 55.3 mmol) and K ₂ CO ₃ (229.37 g, 1,659.6 mmol) were added and the mixture was heated to 150 ° C. with dimethylformamide (2,700 mL). The reaction mixture was stirred for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 112.86 g (yield: 86%) of the product.

(4) Core 2-I-I-I-I-5 and core side 2-5 synthesis

Core side 2-I-5 composite

3-Bromopyridine (220 g, 1.392.4 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) g, 1,670.9 mmol) and _{PdCl 2 (dppf) (34.11 g} , 41.8 mmol) and placed the potassium acetate (409.95 g, 4,177.2 mmol ) in a round bottom flask, into Toluene (7,000 mL) was stirred for 3 hours in 100 ℃. After completion of the reaction, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. After filtration under reduced pressure, the organic layer was dried with MgSO ₄ and concentrated to obtain 242.70 g (yield: 85%) of the product.

Core side 2-5 synthesis

4-bromo-3-iodopyridine (672.0 g, 2,367.1 mmol), Pd (PPh ₃ ) ₄ (41.03 g, 35.5 mmol) and sodium hydroxide were added to the solution of Core side 2-I-5 (242.70 g, (142.03 g, 3,550.7 mmol) were placed in a round-bottomed flask, which was heated to 80 ° C with THF (6,000 mL) and H ₂ O (3,000 mL) and stirred for 6 hours. After the reaction was completed, H ₂ O was removed and the organic layer was concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 172.50 g (yield: 62%) of the product

Core 2-I-I-I-I-5 Synthesis

Core side 2-5 (167.76 g, 713.6 mmol) obtained in the above synthesis was dissolved in THF (3,500 mL), the temperature of the reaction was lowered to -78 ° C, and n-BuLi (70.36 mL, 2.5 M in hexane) After the dropwise addition, the reaction was stirred for 1 hour. Core 2-III-5 (112.86 g, 475.8 mmol) obtained in the above synthesis was dissolved in THF, and the resulting mixture was stirred at room temperature for 4 hours. After completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction mixture was removed. After the filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 144.12 g of the product (yield: 77%).

(5) Core 2-5 Synthesis

Core 2-IIII-5 (144.12 g, 312.2 mmol) obtained in the above synthesis was placed in a round bottom flask and dissolved in acetic acid (1,800 mL). A few drops of HCl were slowly added and stirred at 80 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was neutralized with Na ₂ SO ₄ aqueous solution 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 119.64 g (yield: 87% .

7. Core 4-5 Synthetic example

 (1) Core 4-I-5 synthesis

3-chloro-2H-pyrano [ 3,2-c] pyridin-2-one (150.0 g, 826.1 mmol) into a round bottom flask, 3-chloropyridin-4-amine (169.92 g, 1,321.7 mmol) and Pd _{2 (dba) 3 (22.69 g,} 24.8 mmol) and _{P (t-Bu) 3 (} 13.37 ml, 66.1 mmol) and into the NaOt-Bu (238.18 g, 2,478.2 mmol), was dissolved in toluene (4,000 mL), 110 Lt; 0 &gt; C. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 194.43 g (yield: 86% .

(2) Core 4-I-I-5 synthesis

Into the Core 4-I-5 (194.43 g, 573.5 mmol) obtained in the above synthesis in a round bottom _{flask, Pd (OAc) 2 (2.57} g, 11.5 mmol) and _{P (t-Bu) 3 ·} HBF 4 (16.64 g , 57.3 mmol), and K ₂ CO ₃ (237.78 g, 1,720.4 mmol) were placed in a 500-mL _three- necked flask and stirred with dimethylformamide (2,800 mL) to 150 ° C for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 92.51 g (yield: 68%) of the product.

(3) Core 4-I-I-I-5 synthesis

After dissolving 4-bromopyridine (92.42 g, 585.0 mmol) in THF (3,000 mL), the reaction temperature was lowered to -78 ° C and n-BuLi (57.67 mL, 2.5 M in hexane) was slowly added dropwise. Lt; / RTI &gt; Core 4-II-5 (92.51 g, 390.0 mmol) obtained in the above synthesis was dissolved in THF, injected into the reaction solution, and stirred at room temperature for 4 hours. After the completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction mixture was removed. After the filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 108.55 g of product (yield: 88%).

(4) Core 4-5 Synthesis

4-bromopyridine (81.33 g, 514.7 mmol) was dissolved in THF (3,000 mL), the temperature of the reaction was lowered to -78 ° C and n-BuLi (50.75 mL, 2.5 M in hexane) was slowly added dropwise. Lt; / RTI &gt; Core 4-III-5 (108.55 g, 343.2 mmol) obtained in the above synthesis was dissolved in THF and then poured into the reaction mixture and stirred at room temperature for 4 hours. After the completion of the reaction, water was added to the reaction mixture to quench water. The water in the reaction mixture was removed, and the organic layer was dried over MgSO ₄ and concentrated to obtain 97.70 g (yield: 90%) of the product.

8. Core 5-5 Synthetic example

 (1) Core 5-I-5 synthesis

3-chloropyridin-4-amine (104.08 g, 809.6 mmol) and Pd ₂ (100.0 g, 506.0 mmol) were placed in a round bottom flask, and 3-chloro-2H-thiopyrano [ _{(dba) 3 (13.90 g,} 15.2 mmol) and P (t-Bu) ₃ into the (8.19 ml, 40.5 mmol) and NaOt-Bu (145.89 g, 1,517.9 mmol), was dissolved in toluene (2,500 mL), 110 Lt; 0 &gt; C. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 118.75 g (yield: 81% .

(2) Core 5-I-I-5 synthesis

Pd (OAc) ₂ (1.84 g, 8.2 mmol) and P (t-Bu) _3. HBF ₄ (11.89 g, 8.29 mmol) were placed in a round bottom flask. , 41.0 mmol) and K ₂ CO ₃ (169.94 g, 1,229.6 mmol) were added and the mixture was heated to 150 ° C. with dimethylformamide (2,000 mL), and the reaction mixture was stirred for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 78.89 g (yield: 76%) of the product.

(3) Core 5-I-I-I-5 synthesis

Add Core 5-II-5 (78.89 g, 311.5 mmol), Potassium hydroxide (87.38 g, 1,557.4 mmol), hydrazine monohydrate (311.85 g, 6,229.5 mmol) and ethylene glycol (1,500 mL) And the mixture was stirred for 24 hours while the temperature was raised to 180 ° C. After the reaction was completed, the reaction product was quenched with water, and water in the reaction product was removed. After filtration under reduced pressure, the compound was subjected to silicagel column and recrystallization to obtain 57.39 g of product (yield: 77%).

(4) Core 5-5 Synthetic

Iodomethane (102.12 g, 719.5 mmol), KO (t-Bu) (80.72 g, 719.5 mmol), and dimethylsulfoxide (50 g) were placed in a round bottom flask with the addition of Core 5-III-5 (57.39 g, 239.8 mmol) 1,200 mL) was added, the temperature was increased to 140 캜 and stirred for 24 hours. When the reaction is completed, the reactants are solidified by adding 3 L of water to each of the two 5 L beakers while stirring. Next, the precipitated reaction product was filtered, and only the filtered solid was collected and purified by silicagel column and recrystallized to obtain 45.91 g (yield: 80%) of the product

The compounds belonging to Core 1 may be, but not limited to, the following compounds, and Table 1 shows FD-MS values of the compounds belonging to Core 1.

[Table 1]

II. Synthesis of Sub 1

Sub 1 of Reaction Scheme 1 and Sub 1 of Reaction Scheme 2 may be synthesized as follows but are not limited thereto.

1. Sub 1-7 Synthetic example

1-bromo-4-iodobenzene (338.39 g, 1,196.1 mmol) and K ₂ CO ₃ (100 g, 598.1 mmol) were added to the starting material, 9H- (3.78 g, 5.98 mmol), dibenzo 18-corwn-6 (10.78 g, 29.9 mmol) and nitrobenzene (3,000 ml) were added and heated to 210 ° C and stirred. 19.22 g (yield: 70%) of the product was obtained using the above Sub 2-22 synthesis method. After the reaction was completed, nitrobenezen was removed, and the mixture was extracted with CH ₃ Cl and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 152.23 g of the product (yield: 79%).

2. Sub 1-16 Synthetic example

(1) Sub 1-I-16 synthesis

The starting material, 2,4,6-trichloro-1,3,5-triazine (152.55 g, 827.3 mmol) was dissolved in THF (2,700 ml) in a round bottom flask, the temperature of the reaction was lowered to -78 ° C, Phenylmagnesium bromide (100.0 g, 551.5 mmol) was slowly added dropwise, and the reaction was stirred for 1 hour and then at room temperature for 4 hours. After completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction product was removed. After filtration under reduced pressure, the product was dried with MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 98.49 g (yield: 79% .

(2) Sub 1-16 Synthesis

Sub-1-I-16 (98.49 g, 98.49 mmol) obtained in the above synthesis was placed in a round-bottomed flask and dissolved in THF (240 ml), the temperature of the reaction was lowered to -78 ° C, and [1,1'- 4-ylmagnesium bromide (48.44 g, 188.2 mmol) was slowly added dropwise and the reaction was stirred for 1 hour and then at room temperature for 4 hours. After the reaction was completed, water was added to the reaction mixture to quench water, and the water in the reaction product was removed. The reaction mixture was filtered, and dried over MgSO 4. The resulting product was purified by silicagel column and recrystallized to obtain 131.56 g of product (yield: 61% .

3. Sub 1-28 Synthetic example

The starting material, 2,4-dichlorobenzo [4,5] thieno [ 3,2- d] pyrimidine 4,4,5,5-tetramethyl-2- (naphthalen-2-yl) a (32 g, 125.6 mmol) - 1,3,2-dioxaborolane (35 g, 138 mmol), Pd (PPh 3) 4 (5.80 g, 5.02 mmol), K 2 CO 3 (52 g, 376.41 mmol), THF (440ml), water (220ml) And the temperature of the reaction product is increased to 80 DEG C, followed by stirring for 6 hours. After completion of the reaction, water was removed from the reaction mixture, and the reaction mixture was filtered under reduced pressure, dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 19.58 g of the product (yield: 45%).

4. Sub 1-32 Synthetic example

(1) Sub 1-I-32 synthesis

Bromo-3-chlorobenzene (172.03 g, 898.6 mmol) and Pd ₂ (dba) ₃ (16.46 g, 18.0 mmol) were added to a round-bottomed flask and the starting material, 2-nitrophenyl boronic acid Bu) 3 (17.5 mL, 35.9 mmol) in THF (3,000 mL) and H ₂ O (1,500 mL) were added to the reaction mixture and K ₂ CO ₃ (248.39 g, Slowly. The temperature of the reaction is raised to 80 &lt; 0 &gt; C and the reaction is allowed to stir for 24 hours. After the completion of the reaction, water was removed from the reaction mixture, and the mixture was filtered under reduced pressure, dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 102.18 g of the product (yield: 73%).

(2) Sub 1-I-I-32 synthesis

Sub-1-I-32 (102.18 g, 611.0 mmol) obtained in the above synthesis was placed in a round bottom flask, and triphenylphosphine (400.67 g, 1,527.6 mmol) was added thereto and then heated to 220 ° C. with 1,2-dichlorobenzene The reaction product is stirred for 24 hours while it is dissolved. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, quenched by adding toluene and water, and then water in the reaction mixture was removed. The reaction mixture was filtered under reduced pressure, dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 109.66 g : 0.89%).

(3) Sub 1-I-I-I-32 Synthesis

1-bromo-2-chlorobenzene (156.17 g, 815.7 mmol) and K ₂ CO ₃ (225.48 g, 1,631.4 mmol) were placed in a round-bottomed flask, and Sub 1-II-32 (109.66 g, 543.8 mmol) , Copper (3.46 g, 54.4 mmol), and dibenzo 18-crown-6 (9.80 g, 27.2 mmol) were placed in a reaction vessel and stirred for 24 hours with nitrobenzene (2,700 mL) After the completion of the reaction, the reaction product was quenched by adding water after silicagel filter, and then the water in the reaction product was removed. After filtration under reduced pressure, the product was dried with MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 127.33 g ).

(4) Sub 1-32 Synthesis

Into the Sub 1-III-32 (127.33 g, 407.9 mmol) obtained in the above synthesis in a round bottom _{flask, Pd (OAc) 2 (1.83} g, 8.2 mmol) and _{P (t-Bu) 3 ·} HBF4 (11.83 g, 40.8 mmol) and K ₂ CO ₃ (169.11 g, 1,223.6 mmol), and the mixture was heated to 150 ° C. with dimethylformamide (2,000 mL), and the reaction mixture was stirred for 5 hours. When the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reaction product that has escaped from the filtrate is removed by filtration under reduced pressure, dried over MgSO 4, concentrated The obtained compound was purified by silicagel column and recrystallized to obtain 92.22 g (yield: 82%) of the product.

5. Sub 1-35 Synthetic example

(1) Sub 1-I-35 synthesis

The starting material 2-amino-1-naphthoic acid (75 g, 401 mmol) was added to a round bottom flask with urea (168.7 g, 2808.75 mmol) and stirred at 160 ° C. After confirming the reaction by TLC, the reaction mixture was cooled to 100 ° C, water (200 ml) was added, and the mixture was stirred for 1 hour. When the reaction was completed, the resulting solid was filtered under reduced pressure, washed with water, and dried to obtain 64 g (yield: 76%) of the product.

(2) Sub 1-I-I-35 Synthesis

N , N- Diisopropylethylamine (97.23 g, 752.36 mmol) was slowly added dropwise to the round bottom flask of Sub 1-I-35 (63.86 g, 300.94 mmol) obtained in the above synthesis by dissolving POCl ₃ , And stirred at 90 ° C. After completion of the reaction, the reaction mixture was concentrated, and then ice water (500 ml) was added thereto, followed by stirring at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 68 g of the product (yield: 90%).

(3) Sub 1-35 Synthesis

4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (60.80 g, 297.94 mmol) and Pd (PPh) were added to Sub 1-II-35 (67.47 g, 270.86 mmol) ₃ ) ₄ (12.52 g, 10.83 mmol), K ₂ CO ₃ (112.30 g, 812.57 mmol), THF (950 ml) and water (475 ml) were added. After completion of the reaction, water was removed from the reaction mixture, After drying and concentration, the resulting compound was purified by silicagel column and recrystallized to obtain 45 g of the product (yield: 58%).

The compound belonging to Sub 1 may be, but not limited to, the following compounds, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 1.

[Table 2]

III. Product synthesis

Core 1 (1 eq) was dissolved in toluene in a round bottom flask and Sub 1 (1 eq), Pd ₂ (dba) ₃ (0.03 eq.), (T-Bu) 3P (0.06 eq.) And NaOt-Bu (3 eq.) Were stirred at 100 &lt; 0 &gt; 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 subjected to silicagel column and recrystallization to obtain final product.

1. P 1-1 Synthetic example

Core 1-1 (7.0 g, 18.8 mmol), Sub 1-1 (2.96 g, 18.8 mmol), Pd ₂ (dba) ₃ (0.53 g, 0.6 mmol), (t-Bu) ₃ P (0.31 g, 1.5 mmol) and NaOt-Bu (5.43 g, 56.5 mmol) were dissolved in anhydrous toluene and refluxed for 3 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO _4. After filtration under reduced pressure, the organic solvent was concentrated, and the resulting product was purified by silicagel column and recrystallized to obtain 7.76 g of desired P 1-1. (Yield: 92%)

2. P 1-5 Synthetic example

Core 1-1 (7.0 g, 18.8 mmol), Sub 1-8 (7.45 g, 18.8 mmol), Pd ₂ (dba) ₃ A (0.52 g, 0.6 mmol), (t-Bu) 3 P (0.31 g, 1.5 mmol), NaOt-Bu (5.43 g, 56.5 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 12.41 g of desired P 1-5 was obtained. (Yield: 96%)

3. P 1-8 Synthetic example

Core 1-1 (7.0 g, 18.8 mmol), Sub 1-7 (6.07 g, 18.8 mmol), Pd ₂ (dba) ₃ A (0.52 g, 0.6 mmol), (t-Bu) 3 P (0.31 g, 1.5 mmol), NaOt-Bu (5.43 g, 56.5 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 10.16 g of the desired P 1-8 was obtained. (Yield: 88%).

4. P 1-11 Synthetic example

Core 1-1 (7.0 g, 18.8 mmol), Sub 1-32 (4.46 g, 18.8 mmol), Pd ₂ (dba) ₃ A (0.52 g, 0.6 mmol), (t-Bu) 3 P (0.31 g, 1.5 mmol), NaOt-Bu (5.43 g, 56.5 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 9.59 g of the desired P 1-11 was obtained. (Yield: 89%).

5. P 1-19 Synthetic example

Core 1-1 (7.0 g, 18.8 mmol), Sub 1-75 (5.05 g, 18.8 mmol), Pd ₂ (dba) ₃ A (0.52 g, 0.6 mmol), (t-Bu) 3 P (0.31 g, 1.5 mmol), NaOt-Bu (5.43 g, 56.5 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 9.31 g of the desired P 1-19 was obtained. (Yield: 82%)

6. P 1-24 Synthetic example

Core 1-3 (7.0 g, 18.8 mmol), Sub 1-88 (4.52 g, 18.8 mmol), Pd ₂ (dba) ₃ A (0.52 g, 0.6 mmol), (t-Bu) 3 P (0.30 g, 1.5 mmol), NaOt-Bu (5.42 g, 56.4 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 9.75 g of the desired P 1-24 was obtained. (Yield: 90%).

7. P 1-29 Synthetic example

Core 1-5 (7.0 g, 18.6 mmol), Sub 1-45 (6.64 g, 18.6 mmol), Pd ₂ (dba) ₃ A (0.51 g, 0.6 mmol), (t-Bu) 3 P (0.30 g, 1.5 mmol), NaOt-Bu (5.38 g, 55.9 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 10.49 g of the desired P 1-29 was obtained. (Yield: 81%).

8. P 2-8 Synthetic example

Core 2-6 (7.0 g, 18.1 mmol), Sub 1-49 (5.72 g, 18.1 mmol), Pd ₂ (dba) ₃ A (0.50 g, 0.5 mmol), (t-Bu) 3 P (0.29 g, 1.4 mmol), NaOt-Bu (5.21 g, 54.2 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 10.13 g of the desired P 2-8 was obtained. (Yield: 84%)

9. P 2-15 Synthetic example

Core 2-5 (7.0 g, 18.6 mmol), Sub 1-22 (5.73 g, 18.6 mmol), Pd ₂ (dba) ₃ A (0.51 g, 0.6 mmol), (t-Bu) 3 P (0.30 g, 1.5 mmol), NaOt-Bu (5.38 g, 55.9 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 9.87 g of the desired P 2-15 was obtained. (Yield: 88%).

10. P 3-4 Synthetic example

(1) Core 3-I-3 synthesis

Sub-1-78 (74.67 g, 310.3 mmol), Pd ₂ (dba) ₃ (8.52 g, 9.3 mmol) and P ( t-Bu) ₃ (12.1 ml, 24.8 mmol) and NaOt-Bu (89.45 g, 930.8 mmol) were dissolved in toluene (1,500 mL) and stirred at 110 ° C. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 98.63 g (yield: 87% .

(2) Core 3-I-I-3 synthesis

Core 3-I-3 (98.63 g, 269.9 mmol) obtained in the above synthesis was placed in a round bottom flask and dissolved in CH ₂ Cl ₂ (1,300 mL), followed by stirring at 70 ° C. SOCl ₂ (47.20 g, 396.8 mmol) was slowly added dropwise thereto, followed by stirring for 3 hours. After completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction product was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 91.18 g (yield: 88% .

(3) Core 3-I-I-I-3 synthesis

3-chloropyridin-4-amine (48.86 g, 380.1 mmol) and Pd ₂ (dba) ₃ (6.53 g, 7.17 mmol) were placed in a round bottom flask, and Core 3-II- put mmol) and _{P (t-Bu) 3 (} 9.3 ml, 19.0 mmol) and NaOt-Bu (68.49 g, 712.6 mmol), was dissolved in toluene (1,100 mL), and stirred at 110 ℃. After completion of the reaction, water was added to the reaction mixture to quench water, and water in the reaction product was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 88.19 g (yield: 78% .

(4) Core 3-I-I-I-I-3 synthesis

Pd (OAc) 2 (0.83 g, 3.7 mmol) and P (t-Bu) 3 HBF4 (5.38 g, 3.7 mmol) were added to a round bottom flask, 18.5 mmol), K2CO3 (76.83 g, 555.9 mmol), and the mixture was heated to 150 ° C with dimethylformamide (1,000 mL), and the reaction mixture was stirred for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 70.03 g (yield: 86%) of the product.

 (4) Core 3-I-I-I-I-I-3 synthesis

2-Bromobiphenyl (55.72 g, 239.0 mmol) was dissolved in THF (1,200 mL), the temperature of the reaction was lowered to -78 ° C and n-BuLi (23.56 mL, 2.5M in hexane) was slowly added dropwise. Lt; / RTI &gt; Core 3-IIII-3 (70.03 g, 159.3 mmol) obtained in the above synthesis was dissolved in THF, and the resulting mixture was stirred at room temperature for 4 hours. After the completion of the reaction, water was added to the reaction mixture to quench water. The water in the reaction mixture was removed, and the organic layer was dried over MgSO ₄ and concentrated to obtain 63.38 g of the product (yield: 67%).

(5) Core 3-I-I-I-I-I-I-3 synthesis

Core 3-IIIII-3 (63.38 g, 106.8 mmol) obtained in the above synthesis was dissolved in acetic acid (500 mL) into a round bottom flask, and conc. A few drops of HCl were slowly added and stirred at 80 &lt; 0 &gt; C. After completion of reaction, neutralized with aqueous solution of Na2SO4 and the compound to a silicagel column and the product was recrystallized from 43.02 g (yield: 70%) generates after the organic layer was dried and extracted with water and CH2Cl2 with MgSO ₄ and concentrated to give a.

(6) P 3-4 Synthesis

Sub-1-1 (18.77 g, 119.6 mmol) and Pd ₂ (dba) ₃ (2.05 g, 2.2 mmol) were added to a round bottom flask and Core 3-IIIIII-3 (43.02 g, 74.7 mmol) P (t-Bu) ₃ (1.21 ml, 6.0 mmol) and NaOt-Bu (21.55 g, 224.2 mmol) were placed in toluene (370 mL) and stirred at 110 ° C. After completion of the reaction, the reaction mixture was quenched with water, and the water in the reaction product was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 24.84 g (yield: 51% .

10. P 4-1 Synthetic example

Core 4-1 (7.0 g, 18.7 mmol), Sub 1-27 (6.19 g, 18.7 mmol), Pd ₂ (dba) ₃ A (0.51 g, 0.6 mmol), (t-Bu) 3 P (0.30 g, 1.5 mmol), NaOt-Bu (5.40 g, 56.2 mmol) was dissolved in anhydrous Toluene as after, the same procedure as described in the P 1-1 10.76 g of the desired P 4-1 was obtained. (Yield: 86%)

11. P 4-19 Synthetic example

Core 5-2 (7.0 g, 26.4 mmol), Sub 1-18 (8.50 g, 26.4 mmol), Pd ₂ (dba) ₃ (0.72 g, 0.8 mmol), (t-Bu) ₃ P (0.43 g, 2.1 mmol) and NaOt-Bu (7.61 g, 79.1 mmol) were dissolved in anhydrous toluene, 12.16 g of the desired P 4-19 was obtained. (Yield: 91%).

12. P 5-2 Synthetic example

(1) Synthesis of P 5-I-2

3,6-dichloro-2H-chromen- 2-one (100.0 g, 465.1 mmol) were placed in a round bottom flask, 2-chloroaniline (94.92 g, 744.1 mmol) and _{Pd 2 (dba) 3 (12.78} g, 14.0 mmol ) And P (t-Bu) ₃ (7.53 ml, 37.2 mmol) and NaOt-Bu (134.09 g, 1,395.2 mmol) were dissolved in toluene (2,300 mL) and stirred at 110 ° C. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 52.68 g (yield: 37% .

(2) Synthesis of P 5-I-I-2

Pd (OAc) ₂ (0.77 g, 3.4 mmol) and P (t-Bu) ₃ HBF ₄ (4.99 g, 3.4 mmol) were added to a round bottomed flask. , 17.2 mmol) and K ₂ CO ₃ (71.35 g, 516.3 mmol) were added to the reaction mixture, which was then heated to 150 ° C. with dimethylformamide (860 mL), and the reaction mixture was stirred for 5 hours. After the reaction is completed, the reaction product is concentrated under reduced pressure, quenched by adding water, and filtered to obtain a solid reaction product. The reactant which has escaped from the filtrate is removed by water, filtered under reduced pressure, dried over MgSO ₄ , concentrated The resulting compound was purified by silicagel column and recrystallized to obtain 32.95 g (yield: 71%) of the product.

(3) Synthesis of product side 1-2 with P 1-I-I-I-2

Product side 1-I-2 composite

3-Bromopyridine (50 g, 316.5 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) g, 379.7 mmol), PdCl ₂ (dppf) (7.75 g, 9.5 mmol) and potassium acetate (93.17 g, 949.4 mmol) were placed in a round bottom flask and Toluene (1,500 mL) was added and stirred at 100 ° C for 3 hours. After the reaction was completed, the reaction mixture was quenched with water, and the water in the reaction mixture was removed. After filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 61.0 g (yield: 94%) of the product.

Product side 1-2 Synthetic

The product side 1-I-2 (61.0 g, 297.5 mmol), 1,2-dibromobenzene (140.35 g, 594.9 mmol), Pd (PPh ₃ ) ₄ (10.31 g, 8.9 mmol) and sodium hydroxide the g, 892.4 mmol) into a round bottom flask, and heated to THF (1,500 mL) and _{H 2 O (750 mL) 80} ℃ together, and the mixture was stirred for 6 hours. After the reaction was completed, H ₂ O was removed and the organic layer was concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 57.10 g (yield: 82%) of the product.

P 5-I-I-I-2 synthesis

The product side 1-2 (42.90 g, 183.3 mmol), which is one of the materials obtained in the above synthesis, was dissolved in THF (1,000 mL), the temperature of the reaction was lowered to -78 ° C and n-BuLi hexane) was slowly added dropwise and the reaction was stirred for 1 hour. P 5 II-2 (32.95 g, 122.2 mmol) obtained in the above synthesis was dissolved in THF and then poured into the reaction solution and stirred at room temperature for 4 hours. After the completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction mixture was removed. After the filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 43.09 g of the product (yield: 83%).

(4) P 5 I-I-I-I-2 synthesis

P 5 III-2 (43.09 g, 101.4 mmol) obtained in the above synthesis was dissolved in acetic acid (500 mL) into a round bottom flask, and conc. A few drops of HCl were slowly added and stirred at 80 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was neutralized with aqueous Na ₂ SO ₄ solution 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 35.07 g (yield: 85% .

(5) P 5 I-I-I-I-I-2 synthesis

2-bromobenzene (21.65 g, 137.9 mmol), Pd ₂ (dba) ₃ (2.37 g, 2.6 mmol) and P (2-bromobenzene) were added to a round bottom flask, (t-Bu) ₃ (3.4 ml, 6.9 mmol) and NaOt-Bu (24.85 g, 258.6 mmol) were dissolved in toluene (400 ml) and the mixture was stirred at 110 ° C. After completion of the reaction, water was added to the reaction mixture to quench water, and the water in the reaction product was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 32.47 g (yield: 78% .

(6) P 5-2 Synthesis

Pd ₂ (dba) ₃ (1.85 g, 2.0 mmol) and Core 1-1 (27.47 g, 74.0 mmol) were added to the round bottom flask, and P 5 -IIIII-2 (32.47 g, 67.2 mmol) P (t-Bu) ₃ (2.6 ml, 5.4 mmol) and NaOt-Bu (19.38 g, 201.7 mmol) were placed in toluene (300 mL) and stirred at 110 ° C. After completion of the reaction, the reaction mixture was quenched with water, and the water in the reaction product was removed. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The resulting compound was purified by silicagel column and recrystallized to obtain 42.34 g (yield: 77% .

13. P 5-10 Synthetic example

(1) P 10-I-10 synthesis

Core 1-1 (10 g, 26.9 mmol) and N-bromosuccinimide (5.27 g, 29.6 mmol) were placed in a round bottom flask and methylene chloride (150 mL) and acetic acid (30 mL) were added and stirred at room temperature for 24 hours. After the reaction was completed, water was added to the reaction mixture to neutralize the reaction mixture, and water in the reaction mixture was removed. After the filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 12.61 g of the product (yield: 89%).

(2) P 10-10 Synthesis

(12.61 g, 24.0 mmol), 9,9'-spirobi [fluoren] -4-ylboronic acid (17.26 g, 47.9 mmol) and Pd (PPh ₃ ) ₄ (0.83 g, 0.7 mmol) and sodium hydroxide (2.87 g, 71.9 mmol) were placed in a round bottom flask and heated to 80 ° C with THF (200 mL) and H ₂ O (100 mL) and stirred for 6 hours. After the reaction was completed, H ₂ O was removed, and the organic layer was concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 14.97 g (yield: 82%) of the product

The FD-MS values of the compounds P 1-1 to P 6-5 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

[Table 3]

Evaluation of manufacturing of organic electric device

[ Example  One] Green organic electroluminescent device (Phosphorescent host)

A 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as" 2-TNATA ") film was vacuum deposited on the ITO layer (anode) After the formation of the injection layer, a 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as NPD) film was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, the inventive compound P1-1 was used as a host material and tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) ₃ " (1, 1'-biphenyl-4-olato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter referred to as "BAlq") as a hole blocking layer was formed on the light emitting layer. Was vacuum-deposited to a thickness of 10 nm, and tris- (8-hydroxyquinoline) aluminum (abbreviated as " Alq ₃ " hereinafter) was vacuum deposited as an electron transport layer on the hole blocking layer to a thickness of 40 nm. , An electron injection layer The halogenated alkali metal, an LiF deposited to 0.2 nm thickness, and then Al was prepared as for the organic EL device by forming a negative electrode was deposited in a thickness of 150 nm.

[ Example  2] to [ Example  27]

An organic electroluminescence device was prepared in the same manner as in Example 1, except that the compound of the present invention described in Table 4 was used instead of the compound P1-1 of the present invention as a host material of the light emitting layer.

[ Comparative Example  1] to [ Comparative Example  3]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the following Compounds A to C were used instead of the compound P1-1 of the present invention as a host material in the light emitting layer.

&Lt; Comparative Compound A > < Comparative Compound B > < Comparative Compound C &

Electroluminescence (EL) characteristics were measured with PR-650 manufactured by photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices thus prepared and the comparative organic electroluminescent devices. The measurement result was 5000 cd / m ² standard luminance The T95 lifetime was measured using a lifetime measuring instrument manufactured by McAfee. Table 4 shows the results of device fabrication and evaluation.

[Table 4]

[ Example  28] Red organic electroluminescent device (Phosphorescent host)

A 2-TNATA film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, and then a hole transport layer was formed by vacuum evaporation of the NPD film to a thickness of 60 nm. Then, the compound P1-14 of the present invention was used as a host material on the hole transport layer and bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate (hereinafter referred to as "(piq) ₂ Ir (acac) Was doped at a weight ratio of 95: 5 to deposit a light emitting layer with a thickness of 30 nm. Subsequently, BAlq was vacuum deposited as a hole blocking layer on the light emitting layer to a thickness of 10 nm, and Alq ₃ was vacuum deposited as an electron transporting layer on the hole blocking layer to a thickness of 40 nm. Then, an organic electroluminescence device was prepared by depositing LiF, an alkali metal halide, as an electron injection layer to a thickness of 0.2 nm, and then depositing Al to a thickness of 150 nm to form a cathode.

[ Example  29] to [ Example  36]

An organic electroluminescent device was prepared in the same manner as in Example 28 except that the compound of the present invention described in Table 5 was used instead of the compound P1-14 of the present invention as a host material of the emitting layer.

[ Comparative Example  4] to [ Comparative Example  6]

An organic electroluminescent device was fabricated in the same manner as in Example 28 except that the above Comparative Compounds A to C were used instead of the compound P1-14 of the present invention as a host material in the light emitting layer.

Electroluminescence (EL) characteristics were measured with PR-650 manufactured by photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices thus manufactured and the comparative organic electroluminescence devices, and the measured luminance was 2500 cd / m ² standard luminance The T95 lifetime was measured using a lifetime measuring instrument manufactured by McAfee. Table 5 shows the results of device fabrication and evaluation.

[Table 5]

As can be seen from the results of Tables 4 and 5, the organic electroluminescent device using the organic electroluminescent device material of the present invention as a phosphorescent host has remarkably improved luminous efficiency, lifetime and driving voltage.

The result of the organic electronic device using the comparative compound 2 and the comparative compound 3 which are quadruple ring compounds, rather than the comparative compound 1, which is the CBP mainly used as the host material, was better, The driving voltage, the efficiency, and the lifetime of the organic electroluminescent device using the compound of the present invention containing an element-substituted hemi-ring were the best.

This means that the compounds of the present invention, which necessarily contain a heterocycle substituted with a heteroatom in the core, have a wide band gab and a suitable energy level (e.g. HOMO, LUMO, T1) Layer, it is considered that the driving voltage, efficiency, and lifetime of the device are improved because it acts as a main factor (eg, energy balance, hole mobility, and electron mobility)

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 (11)

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

In the above formulas,
Z ¹ to Z ⁸ independently of one another are C (R ₀ ) or N,
Wherein R &lt; ₀ &gt; is independently selected from the group consisting of 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 fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); adjacent R ₀ may be bonded to each other to form a ring,
X ¹ and X ² are independently of each other a single bond, NR ', O or S,
R 'is hydrogen; A C ₁ to C ₅₀ alkyl group; A C ₆ to C ₆₀ aryl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b );
Ar ¹ and Ar ² are each independently 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 fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); Ar ¹ and Ar ² may combine with each other to form a ring,
L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A 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 C ₂ to C ₆₀ heterocyclic group,
R _a and R _b are each independently a C ₆ to C ₆₀ aryl group; A fluorenyl group; A 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 C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P;
Wherein R _0, R ', Ar ^1, Ar ^2, L', R ^a and R ^b is one bonded to each other adjacent R ₀ together a ring, formed by the Ar ¹ and Ar ² formed by combining each other ring are each deuterium ; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; Aryl alkenyl group of C ₈ -C _20; A C ₆ -C ₃₀ aryloxy group; And a combination of these. The method according to claim 1,
(1) is represented by one of the following Chemical Formulas (2) to (10):
&Lt; Formula 2 >< EMI ID =

&Lt; Formula 5 &gt;&lt; EMI ID =

&Lt; Formula 8 >< EMI ID =

Wherein Ar ¹ , Ar ² , Z ¹ to Z ⁸ are as defined in claim 1,
L ¹ and L ² independently of one another are a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A 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 C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P;
Ar ⁴ and Ar ⁵ are each independently 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 fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); and L ', R _a and R _b are as defined in claim 1. The method according to claim 1,
And at least one of Z ¹ to Z ⁸ is N. The method according to claim 1,
Wherein R 'is represented by one of the following formulas A-1 to A-5:
<Formula A-1><FormulaA-2><FormulaA-3>

&Lt; Formula A-4 >< Formula A-5 &

In the above formulas,
L is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A 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 C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P;
At least one of X ¹ to X ²² is N and the others are C (R ¹ )
R &lt; ¹ &gt; is hydrogen; heavy hydrogen; halogen; A C ₆ to C ₂₀ aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one hetero atom in the P C _20; 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 ₁ to C ₂₀ alkoxyl group; And an aryloxy group having ₆ to ₃₀ carbon atoms, and adjacent R &lt; ¹ &gt; s may be bonded to each other to form a ring,
Ar ⁶ is a C ₆ to C ₂₀ aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one hetero atom in the P C _20; 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 ₁ to C ₂₀ alkoxyl group; And an aryloxy group having from ₆ to ₃₀ carbon atoms,
F ¹ and F ² are, independently of each other N (R ^1), S, O or ^{C (R 1) (R 2} ), a and b is an integer of 0 or 1, a + b is an integer of 1 or more,
R ¹ and R ² are independently of each other hydrogen; An alkyl group having ₁ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; And a C ₂ to C ₂₀ heterocyclic group containing at least one hetero atom selected from the group consisting of O, N, S, Si and P, and R ¹ and R ² are bonded to each other to form a spiro compound can do. The method according to claim 1,
Wherein the compound of formula (I) is one of the following compounds:

. A first electrode; A second electrode; And an organic material layer formed between the first electrode and the second electrode and containing a compound according to any one of claims 1 to 5. The method according to claim 6,
Wherein the organic material layer includes at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting auxiliary layer, an electron transporting layer and an electron injecting layer,
It is preferable that the compound is at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting supporting layer, an electron transporting layer and an electron injecting layer in the form of a single compound or a mixture of two or more compounds An organic electric device characterized by: 8. The method of claim 7,
Wherein the compound is used as a phosphorescent host material of the light emitting layer. The method according to claim 6,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device including the organic electroluminescent device of claim 6; And
And a control unit for driving the display device. 11. The method of claim 10,
Wherein the organic electroluminescent device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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