KR102128338B1 - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

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

Description

Compound for organic electric element, organic electric element using the same, and electronic device therefor{COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND A ELECTRONIC DEVICE THEREOF}

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

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

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

On the other hand, the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electric device, delays the diffusion and diffusion of the metal oxide into the organic layer. There is a need to develop a hole injection layer material having a temperature. In addition, the low glass transition temperature of the hole transport layer material has been reported to have a great influence on the device life depending on the property that the uniformity of the thin film surface collapses when driving the device. In addition, in the formation of OLED devices, the deposition method is predominant, and a material capable of withstanding such a deposition method for a long time, that is, a material having strong heat resistance characteristics is required.

In order to sufficiently exhibit the excellent characteristics of the above-mentioned organic electric device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material, are supported by stable and efficient materials It should be preceded, but the development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently performed, and therefore, the development of a new material is still required.

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

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

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

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

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

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

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

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

On the other hand, the term "halo" or "halogen" as used herein has no other description.

One fluorine, chlorine, bromine, and iodine.

The term "alkyl" or "alkyl group" used in the present invention has 1 to 60 carbon atoms, and is not limited thereto unless otherwise specified.

The terms "alkenyl" or "alkynyl" used in the present invention have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise specified, and are not limited thereto.

The term "cycloalkyl" used in the present invention means alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto. The term "alkoxy group" used in the present invention has 1 to 60 carbon atoms, and is not limited thereto, unless otherwise specified.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto.

In the present invention, an aryl group or an arylene group refers to a monocyclic or heterocyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, biphenyl group, fluorene group, or spirofluorene group.

As used herein, the term "heteroalkyl" means alkyl containing one or more heteroatoms, unless otherwise specified. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 3 to 60 carbon atoms each containing at least one hetero atom, unless otherwise specified, and is limited thereto No, it contains a heterocycle as well as a single ring, and may be formed by combining adjacent groups.

The terms "heterocycloalkyl" and "heterocyclic group" used in the present invention include one or more heteroatoms, have 2 to 60 carbon atoms, and include heterocycles as well as monocycles unless otherwise specified. , Adjacent groups may be formed by combining. In addition, "heterocyclic group" may mean an alicyclic and/or aromatic group containing heteroatoms.

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

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

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

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

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C ₅ to C ₂₀ heterocyclic groups, and is not limited to these substituents.

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

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180 and a first electrode 110 and a second electrode 180 formed on the substrate 110. ) Is provided with an organic material layer containing the compound represented by Formula 1. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may sequentially include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170 on the first electrode 120. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160, etc. may also serve as a hole blocking layer.

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

The compound according to the present invention applied to the organic material layer is the material of the host or dopant or capping layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, and the light emitting layer 150 Can be used as

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

In addition, the organic material layer is less by a method such as a solution process or a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer), which is not a vapor deposition method using various polymer materials. It can be prepared by a number of layers. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.

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

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

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

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

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

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₁₀ are ⅰ) independently of each other, hydrogen, deuterium, halogen, C ₆ ~ C ₆₀ aryl group, a fluorenyl group, a fused aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C ₆₀ C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of a ring group, O, N, S, Si and P, -LN(R')(R"), C ₁ ~ C ₅₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₃₀ alkoxy group and may be selected from the group consisting of C ₆ ~ C ₃₀ aryloxy group, provided that X is S or O, or Y is S or In the case of O, R ₁ to R ₄ and R ₇ to R ₁₀ cannot both be hydrogen at the same time, for example, when X is S, R ₁ to R ₄ and R ₇ to R ₁₀ At least one of them cannot be hydrogen, and when Y is O, at least one of R ₁ to R ₄ and R ₇ to R ₁₀ cannot be hydrogen.

Or they may ii) combine adjacent groups with each other to form at least one ring, wherein groups not forming a ring are as defined in iii).

Here, "to form at least one ring bonded to each other adjacent to each other a group" means any R ₁ and R ₂ together, R ₂ and R ₃ together and / or R ₃ and R ₄ at least one ring by combining to each other, It means forming a compound. At this time, since it is important that neighboring groups combine with each other to form a ring, the scope of the present invention is not limited by what substituents they are and through which reaction the ring is formed. At this time, the ring is another known reaction (Heck reaction or Chem. Eur. J. 2009, 15, 742, Molecules. 2008, 13, 3236-3245, J. Am. Chem. Soc. 2008, 130, 472-480, Tetrahedron Letters. 1997, 38, 4761-4764, etc.).

The ring formed by combining adjacent groups among R ₁ to R ₁₀ may be a monocyclic or polycyclic aromatic ring or a heterocyclic ring including at least one hetero atom, or may be a fused aromatic ring and an aliphatic ring. Illustratively, adjacent groups among R ₁ and R _{4 may} be combined with each other to form an aromatic ring such as benzene, naphthalene, and phenanthrene, wherein the number of nuclear carbon atoms in the aromatic ring formed is preferably 6 to 60. For example, when R ₁ and R ₂ are combined with each other to form a benzene ring, and R ₃ and R ₄ are combined with each other to form a benzene ring, the phenanthrene form may be formed together with the benzene ring of the parent nuclei to which they are bonded.

In addition, adjacent groups among R ₁ to R _{10 may} be bonded to each other to form a heterocycle such as thiophene, furan, pyridine, indole, quinoline, etc., wherein the number of nuclear carbon atoms may be 2 to 60. In addition, in the case of a polycyclic ring, it may be a fused form, a plurality of rings may be a form that is not fused to each other, or a ring in which a fused form and a non-fused form are mixed.

X and Y are each independently S, O, C(R ₁₁ )(R ₁₂ ) or Si(R ₁₁ )(R ₁₂ ), and m and n are each 0 or 1. However, it must be an integer greater than or equal to m+n=1, that is, n is 0 when m is 1, and n is 1 when m is 0. And here, R ₁₁ And R ₁₂ are independently of each other hydrogen, a C ₆ ~ C ₆₀ aryl group, O, N, S, Si and P containing at least one heteroatom heterocyclic group of C ₂ ~ C ₆₀ , -LN (R ') (R") or C ₁ ~ C _{50 It} may be an alkyl group.

L is a direct bond; C ₆ ~ C ₆₀ Arylene group; Fluorylene group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And divalent aliphatic hydrocarbon group; may be selected from the group consisting of. At this time, the arylene group, fluorene group, heterocyclic group and aliphatic hydrocarbon group are nitro group, cyano group, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ hetero It may be substituted with one or more substituents selected from the group consisting of a cyclic group, a C ₁ ~C ₂₀ alkoxy group, and an amino group.

The direct bond means that L is absent, and referring to Chemical Formulas 1-1 and 1-11 of the present invention, it can be seen that L is absent.

Ar ₁ is hydrogen, deuterium, tritium, halogen, a C ₆ ~ C ₆₀ aryl group, O, N, S, Si and P containing at least one heteroatom heterocyclic group of C ₂ ~ C ₆₀ , flu Orenyl group, C ₁ ~ C ₅₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₃₀ alkoxyl group and -N (R') (R") is selected from the group consisting of,

R'and R" are independently of each other O, N, S, Si and P, C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom, C ₆ ~ C ₆₀ aryl group, C ₁ ~ C ₅₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group or a fluorenyl group.

Meanwhile, R ₁ to R ₁₂ , Ar ₁ , R'and R" may be further substituted with other substituents.

When R ₁ to R ₁₂ , Ar ₁ , R'and R" are aryl groups, they are deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ to C ₂₀ alkylthio, C ₁ ~ C ₂₀ Alkoxy group, C ₁ ~ C ₂₀ Alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl), C ₂ ~ C ₂₀ alkynyl group (alkynyl), C ₆ ~ C ₂₀ aryl group , C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₁ to R ₁₂ , Ar ₁ , R'and R" are heterocyclic groups, they are deuterium, halogen, silane group, cyano group, nitro group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a heterocyclic group of _{C 2 ~ C 20, C 3} ~ C ₂₀ cycloalkyl group, C ₇ ~C ₂₀ of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₁ to R ₁₀ , Ar ₁ , R'and R" are fluorenyl groups, they are deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group ( alkenyl), C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₂ ~ C ₂₀ of the heterocyclic group and C ₃ ~ C ₂₀ from the group consisting of a cycloalkyl group at least one group selected in the It may be substituted with a substituent.

And when R ₁ ~ R _1O is a fused ring group, it is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ ~ C ₂₀ alkylthio, C ₁ ~ C ₂₀ alkoxy Actual group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl), C ₂ ~ C ₂₀ alkynyl group (alkynyl), C ₆ ~ C ₂₀ aryl group, C ₆ substituted with deuterium ~ C ₂₀ Aryl group, C ₂ ~ C ₂₀ Heterocyclic group, C ₃ ~ C ₂₀ Cycloalkyl group, C ₇ ~ C ₂₀ Of It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₁ ~ R ₁₂ is an alkyl group, it is a halogen, silane group, boron group, cyano group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl group) ), a C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₇ ~ C ₂₀ substituted by deuterium It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~ C ₂₀ arylalkenyl groups,

When R ₁ ~ R ₁₀ is an alkenyl group, it is deuterium, halogen, silane group, cyano group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group (alkenyl group) ), a C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ aryl group substituted with a heavy hydrogen, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of the It may be substituted with one or more substituents selected from the group consisting of arylalkyl groups and C ₈ ~C ₂₀ arylalkenyl groups.

Further, when the R ₁ ~ R ₁₀ is an alkoxyl group, it is deuterium, halogen, silane group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ aryl substituted with deuterium Group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group may be substituted with one or more substituents selected from the group consisting of,

Wherein R ₁ ~ R ₁₀ is an aryloxy group cases, this deuterium, a silane group, a cyano group, C of ₁ ~ C ₂₀ alkyl group, a C ₆ ~ C ₂₀ substituted with an aryl group, a heavy hydrogen of C ₆ ~ C ₂₀ aryl group , C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group may be substituted with one or more substituents selected from the group consisting of.

Meanwhile, the compound represented by Chemical Formula 1 may be represented by Chemical Formula 2 or Chemical Formula 3.

<Formula 2> <Formula 3>

In the above formula, X, Y, R ₁ to R ₁₀ , L and Ar ₁ are as defined in Formula 1.

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

<Formula 4> <Formula 5> <Formula 6>

<Formula 7> <Formula 8> <Formula 9>

<Formula 10> <Formula 11> <Formula 12> <Formula 13>

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

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

<Formula 20> <Formula 21> <Formula 22> <Formula 23>

In the above formula, X, Y, R ₁ to R4, R ₅ , R ₆ , L and Ar ₁ are as defined in Formula 1.

Meanwhile, Chemical Formula 1 may be represented by the following compounds.

Hereinafter, examples of the synthesis of the compound represented by Chemical Formula 1 according to the present invention and the manufacturing example of the organic electric device will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

Synthetic example

Illustratively, a compound according to the present invention (final products) is prepared by reacting one of Sub 1 to Sub 22 with Sub 23 as shown in Reaction Scheme 1 below.

<Scheme 1>

[ Example One]

One. Sub Synthesis of 1

Sub 1 may be synthesized by the reaction route of Scheme 2 below.

<Reaction Scheme 2>

(One) Sub 1-2 Synthetic example

Sub 1-1 was dissolved in a carbon disulfide solvent under nitrogen, and bromine was slowly added dropwise. After stirring at room temperature for 12 hours, when the reaction was completed, the organic solvent was concentrated using a decompression device, and the resulting product was recrystallized using an ethanol solvent to obtain the desired Sub 1-2.

(2) Sub 1-3 Synthetic example

The obtained Sub 1-2 was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was stirred at 0 °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 1-3.

(3) Sub 1-4 Synthetic example

The obtained Sub 1-3 and 1-iodo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 1-4.

(4) Sub One Synthetic example

The obtained Sub 1-4 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 1.

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

[Table 1]

[ Example 2]

One. Sub 2 Synthesis

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 3 below.

<Scheme 3>

(One) Sub 2-2 Synthetic example

Sub 2-1 was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78°C, n-BuLi (2.5M in hexane) was slowly added dropwise, and the reaction was stirred at 0°C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 2-2 using column chromatography.

(2) Sub 2-3 Synthetic example

Sub 2-2 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ substituted with R ₁ to R ₄ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing the water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to obtain the desired Sub 2-3 using column chromatography.

(3) Sub 2 Synthetic example

Sub 2-3 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 2.

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

[Table 2]

[ Example 3]

One. Sub 3 Synthesis

Sub 3 may be synthesized by the reaction route of Scheme 4 below.

<Reaction Scheme 4>

(One) Sub 3-1 Synthetic example

Add 4-bromonaphthalen-1-ylboronic acid and (2-bromophenyl)(methyl)sulfane and tetrakis(triphenylphophine)palladium(0) and potassium carbonate substituted with R ₇ to R ₁₀ , THF (tetrahydrofuran) and water (3:1) was added and stirred at 70°C. Upon completion of the reaction, extract with CH ₂ Cl ₂ , wipe with water, remove a small amount of water with anhydrous MgSO ₄ , filter under reduced pressure, concentrate the organic solvent, and recrystallize the resulting product using CH ₂ Cl ₂ and hexane solvent. The desired Sub 3-1 was obtained.

(2) Sub 3-2 Synthetic example

Sub 3-1 is dissolved in acetic acid, and hydrogen peroxide dissolved in acetic aicd is dropped dropwise and stirred at room temperature for 6 hours. When the reaction was completed, acetic acid was removed using a pressure-reducing device and separated using column chromatography to obtain a desired Sub 3-2.

(3) Sub 3-3 Synthetic example

Put the obtained Sub 3-2 and trifluoromethanesulfonic acid (trifluoromethanesulfonic acid) and stirred at room temperature for 24 hours, then slowly add water and pyridine (8:1) (pyridine (8:1)) and reflux for 30 minutes. Lower the temperature, extract with CH ₂ Cl ₂ and wipe with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 3-3.

(4) Sub 3-4 Synthetic example

After dissolving the obtained Sub 3-3 and R _{1 ~} a 1-bromo-2-nitrobenzene, Pd (PPh 3) 4 is substituted by _4, K ₂ CO ₃ in dry THF and a small amount of water and the mixture was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 3-4.

(5) Sub 3 Synthetic example

The obtained Sub 3-4 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 3.

[ Example 4]

One. Sub 4 Synthesis

Sub 4 may be synthesized by the reaction route of Scheme 5 below.

<Reaction Scheme 5>

(One) Sub 4-1 Synthetic example

5-bromobenzo[b]naphtho[2,1-d]thiophene substituted with R _{7 ~10} was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78°C, and n-BuLi (2.5 M inhexane) was slowly added dropwise. After that, the reaction was stirred at 0° C. for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 4-1.

(2) Sub 4-2 Synthetic example

After dissolving the obtained Sub 4-1 and R _{1 ~} a 1-bromo-2-nitrobenzene, Pd (PPh 3) 4 is substituted by _4, K ₂ CO ₃ in dry THF and a small amount of water and the mixture was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 4-2.

(3) Sub 4 Synthetic example

The obtained Sub 4-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 4.

[ Example 5]

One. Sub 5 Synthesis

Sub 5 may be synthesized by the reaction route of Scheme 6 below.

<Scheme 6>

(One) Sub 5-1 Synthetic example

5-bromobenzo[b]naphtho[2,1-d]thiophene was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was then 0 °C. The mixture was stirred for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 5-1.

(2) Sub 5-2 Synthetic example

The obtained Sub 5-1 and 1-bromo-2-nitronaphthalene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 5-2.

(3) Sub 5 Synthetic example

The obtained Sub 5-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 5.

[ Example 6]

One. Sub 6 Synthesis

Sub 6 may be synthesized by the reaction route of Scheme 7 below.

<Scheme 7>

(One) Sub 6-1 Synthetic example

After dissolving 5-bromobenzo[d]naphtho[2,1-b]thiophene and 1-bromo-2-nitronaphthalene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ in anhydrous THF and a small amount of water, for 24 hours Refluxed. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 6-1.

(2) Sub 6 Synthetic example

The obtained Sub 6-1 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 6.

[ Example 7]

One. Sub 7 Synthesis

Sub 7 may be synthesized by the reaction route of Scheme 8 below.

<Scheme 8>

(One) Sub 7-1 Synthetic example

5-bromobenzo[b]naphtho[2,1-d]thiophene was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was then 0 °C. The mixture was stirred for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 7-1.

( 2) Sub 7-2 Synthetic example

The obtained Sub 7-1 and 9-bromo-10-nitrophenanthrene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 7-2.

( 3) Sub 7 Synthetic example

The obtained Sub 7-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 7.

[ Example 8]

One. Sub 8 Synthesis

Sub 8 may be synthesized by the reaction route of Scheme 9 below.

<Scheme 9>

(One) Sub 8-1 Synthetic example

5-bromobenzo[d]naphtho[2,1-b]thiophene was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was then 0 °C. The mixture was stirred for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 8-1.

( 2) Sub 8-2 Synthetic example

The obtained Sub 8-1 and 9-bromo-10-nitrophenanthrene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 8-2.

( 3) Sub 8 Synthetic example

The obtained Sub 8-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 8.

[ Example 9]

One. Sub 9 Synthesis

Sub 9 may be synthesized by the reaction route of Scheme 10 below.

<Reaction Scheme 10>

( 1) Sub 9-1 Synthetic example

2-bromodibenzo[b,d]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reactant was 0. It was stirred for 1 hour at ℃. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 9-1.

( 2) Sub 9-2 Synthetic example

The obtained Sub 9-1 and 1-bromo-2-nitronaphthalene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 9-2.

( 3) Sub 9 Synthetic example

The obtained Sub 9-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 9.

[ Example 10]

One. Sub 10 Synthesis

Sub 10 may be synthesized by the reaction route of Reaction Scheme 11 below.

<Scheme 11>

( 1) Sub 10-1 Synthetic example

3-bromodibenzo[b,d]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reactant was 0. It was stirred for 1 hour at ℃. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 10-1.

( 2) Sub 10-2 Synthetic example

The obtained Sub 10-1 and 1-bromo-2-nitronaphthalene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 10-2.

( 3) Sub 10 Synthetic example

The obtained Sub 10-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 10.

[ Example 11]

One. Sub 11 Synthesis

Sub 11 may be synthesized by the reaction route of Reaction Scheme 12 below.

<Reaction Scheme 12>

( 1) Sub 11-1 Synthetic example

2-bromodibenzo[b,d]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reactant was 0. It was stirred for 1 hour at ℃. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 11-1.

( 2) Sub 11-2 Synthetic example

The obtained Sub 9-1 and 9-bromo-10-nitrophenanthrene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product by column chromatography to obtain the desired Sub 11-2.

( 3) Sub 11 Synthetic example

The obtained Sub 11-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 11.

[ Example 12]

One. Sub 12 Synthesis

Sub 12 may be synthesized by the reaction route of Scheme 13 below.

<Scheme 13>

( 1) Sub 12-1 Synthetic example

3-bromodibenzo[b,d]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78 °C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reactant was 0. It was stirred for 1 hour at ℃. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 12-1.

( 2) Sub 12-2 Synthetic example

The obtained Sub 12-1 and 9-bromo-10-nitrophenanthrene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 12-2.

( 3) Sub 12 Synthetic example

The obtained Sub 12-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 12.

[ Example 13]

One. Sub 13 Synthesis

Sub 13 may be synthesized by the reaction route of Scheme 14 below.

<Reaction Scheme 14>

( 1) Sub 13-1 Synthetic example

After dissolving 5-bromodinaphtho[1,2-b:2',1'-d]thiophene in anhydrous THF, lowering the temperature of the reactant to -78 °C and slowly adding n-BuLi (2.5 M inhexane), The reaction was stirred at 0 °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 13-1.

( 2) Sub 13-2 Synthetic example

The obtained Sub 13-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 13-2.

( 3) Sub 13 Synthetic example

The obtained Sub 13-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 13.

[ Example 14]

One. Sub 14 Synthesis

Sub 14 may be synthesized by the reaction route of Scheme 15 below.

<Reaction Scheme 15>

( 1) Sub 14-1 Synthetic example

After dissolving 5-bromodinaphtho[2,1-b:1',2'-d]thiophene in anhydrous THF, lowering the temperature of the reactant to -78 ℃, slowly adding n-BuLi (2.5 M inhexane), and The reaction was stirred at 0 °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 14-1.

( 2) Sub 14-2 Synthetic example

The obtained Sub 14-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 14-2.

( 3) Sub 14 Synthetic example

The obtained Sub 14-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 14.

[ Example 15]

One. Sub 15 Synthesis

Sub 15 may be synthesized by the reaction route of Reaction Scheme 16 below.

<Reaction Scheme 16>

( 1) Sub 15-1 Synthetic example

After 14-bromonaphtho[2,1-d]phenanthro[9,10-b]thiophene was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78°C, n-BuLi (2.5 M inhexane) was slowly added dropwise, The reaction was stirred at 0 °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction mixture with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 15-1.

( 2) Sub 15-2 Synthetic example

The obtained Sub 15-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 7-2.

( 3) Sub 15 Synthetic example

The obtained Sub 15-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 15.

[ Example 16]

One. Sub 16 synthesis

Sub 16 may be synthesized by the reaction route of Scheme 17 below.

<Reaction Scheme 17>

( 1) Sub 16-1 Synthetic example

After dissolving 5-bromonaphtho[2,1-b]phenanthro[9,10-d]thiophene in anhydrous THF, lowering the temperature of the reactant to -78 ℃, slowly adding n-BuLi (2.5 M inhexane), and The reaction was stirred at 0 °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 16-1.

( 2) Sub 16-2 Synthetic example

The obtained Sub 16-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 16-2.

( 3) Sub 16 Synthetic example

The obtained Sub 16-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 8.

[ Example 17]

One. Sub 17 Synthesis

Sub 17 may be synthesized by the reaction route of Scheme 18 below.

<Reaction Scheme 18>

( 1) Sub 17-1 Synthetic example

Dissolve 8-bromobenzo[d]naphtho[1,2-b]thiophene substituted with R _{5 ~6} in anhydrous THF, lower the temperature of the reactant to -78 ℃, slowly drop n-BuLi (2.5 M inhexane) After that, the reaction was stirred at 0° C. for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 17-1.

( 2) Sub 17-2 Synthetic example

The obtained Sub 17-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 17-2.

( 3) Sub 17 Synthetic example

The obtained Sub 17-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 17.

[ Example 18]

One. Sub 18 Synthesis

Sub 18 can be synthesized by the reaction route of Scheme 19 below.

<Scheme 19>

( 1) Sub 18-1 Synthetic example

It is dissolved in a 9-bromobenzo [b] naphtho [ 1,2-d] thiophene substituted with R _{5 ~ 6} in anhydrous THF, cooled the reaction to -78 ℃, was added dropwise n-BuLi (2.5 M inhexane) slowly and After that, the reaction was stirred at 0° C. for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 18-1.

( 2) Sub 18-2 Synthetic example

The obtained Sub 18-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 18-2.

( 3) Sub 18 Synthetic example

The obtained Sub 18-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 18.

[ Example 19]

One. Sub 19 Synthesis

Sub 19 may be synthesized by the reaction route of Scheme 20 below.

<Reaction Scheme 20>

( 1) Sub 19-1 Synthetic example

12-bromobenzo[d]phenanthro[9,10-b]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78°C, and n-BuLi (2.5 M inhexane) was slowly added dropwise. After that, the reaction was stirred at 0° C. for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 19-1.

( 2) Sub 19-2 Synthetic example

The obtained Sub 19-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 19-2.

( 3) Sub 19 Synthetic example

The obtained Sub 19-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 19.

[ Example 20]

One. Sub 20 synthetic

Sub 20 may be synthesized by the reaction route of Reaction Scheme 21 below.

<Reaction Scheme 21>

( 1) Sub 20-1 Synthetic example

11-bromobenzo[b]phenanthro[9,10-d]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reactant was lowered to -78°C, and n-BuLi (2.5 M inhexane) was slowly added dropwise. After that, the reaction was stirred at 0° C. for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 20-1.

( 2) Sub 20-2 Synthetic example

The obtained Sub 20-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 20-2.

( 3) Sub 20 Synthetic example

The obtained Sub 20-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 20.

[ Example 21]

One. Sub 21 Synthesis

Sub 21 may be synthesized by the reaction route of Scheme 22 below.

<Reaction Scheme 22>

( 1) Sub 21-2 Synthetic example

After dissolving the Sub 21-1 and R _{1 ~} a 1-bromo-2-nitrobenzene, Pd (PPh 3) is substituted by _{4 4,} K ₂ CO ₃ in dry THF and a small amount of water and the mixture was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 21-2.

( 2) Sub 21 Synthetic example

The obtained Sub 21-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired Sub 21.

[ Example 22]

One. Sub 22 Synthesis

Sub 22 may be synthesized by the reaction route of Scheme 23 below.

<Scheme 23>

( 1) Sub 22-1 Synthetic example

Dissolve 5-bromo-11,11-dimethyl-11H-benzo[a]fluorene substituted with R _{7 ~10} in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly decrease n-BuLi (2.5 M inhexane). After dropwise addition, the reaction was stirred at 0° C. for 1 hour. Thereafter, the temperature of the reactant was lowered to -78°C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, a 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing water in the reaction with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 22-1.

( 2) Sub 22-2 Synthetic example

After dissolving the obtained Sub 22-1 and R _{1 ~} a 1-bromo-2-nitrobenzene, Pd (PPh 3) 4 is substituted by _4, K ₂ CO ₃ in dry THF and a small amount of water and the mixture was refluxed for 24 hours. When the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. After removing a small amount of water with anhydrous MgSO ₄ and filtering under reduced pressure, the organic solvent was concentrated to separate the resulting product using column chromatography to obtain the desired Sub 22-2.

( 3) Sub 22 Synthetic example

The obtained Sub 22-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain a desired Sub 22.

[ Example 23]

Sub 23 Example

Examples of Sub 23 are as follows, but are not limited thereto, and their FD-MS values are shown in Table 3.

[Table 3]

[ Example 24]

Products Synthetic example

One of Sub 1 to Sub 22 (1 eq) and Sub 23 (1.1 eq) obtained in the above synthesis were added to toluene and Pd ₂ (dba) ₃ (0.05 eq), PPh ₃ (0.1 eq.) and NaO t -Bu (3 eq.) were added respectively, followed by reflux with stirring at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was obtained by silicagel column and recrystallization.

(One) Product 1-1 Synthetic example

<Reaction Scheme 24>

After mixing the five-membered hetero compound (5.5g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and stirred and refluxed at 100°C for 24 hours . After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 4.8 g of product 1-1 (68% yield).

( 2)Product 2-6 Synthetic example

<Reaction Scheme 25>

After mixing the five-membered hetero compound (12.7g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and stirred and refluxed at 100° C. for 24 hours. . After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 9.2 g of product 2-7 (yield 65%).

( 3)Product 3-9 Synthetic example

<Reaction Scheme 26>

After mixing the five-membered hetero compound (7.7g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and stirred and refluxed at 100° C. for 24 hours. . After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 6.1g of product 3-9 (yield 66%).

( 4)Product 4-15 Synthetic example

<Reaction Scheme 27>

After mixing the five-membered hetero compound (8.0g, 20mmol) and the substituted pyridine compound (7.5g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and then at 100° C. for 24 hours. It was stirred and refluxed. After extraction with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.9 g of product 4-15 (yield 63%).

( 5)Product 5-11 Synthetic example

<Reaction Scheme 28>

After mixing the five-membered hetero compound (7.5g, 20mmol) and 5-bromo-2,4-diphenylpyrimidine (7.5g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively. The mixture was stirred and refluxed at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.7 g of product 5-11 (yield 64%).

( 6)Product 6-14 Synthetic example

<Scheme 29>

After mixing the five-membered hetero compound (7.5g, 20mmol) and 4-(4-bromophenyl)-2,6-diphenylpyrimidine (9.3g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were respectively added. After the addition, the mixture was stirred and refluxed at 100°C for 24 hours. After extracting with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 8.8 g of product 6-14 (yield 65%).

( 7)Product 7-2 Synthetic example

<Scheme 30>

After mixing the five-membered hetero compound (8.5g, 20mmol) and 2-bromonaphthalene (5.0g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added respectively, followed by stirring at 100° C. for 24 hours. Let it reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.7 g of product 7-2 (yield 70%).

( 8)Product 8-8 Synthetic example

<Scheme 31>

After mixing the five-membered hetero compound (8.5g, 20mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , NaOt After each addition of -Bu, the mixture was refluxed with stirring at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 8.6 g (yield 66%) of product 8-8.

( 9)Product 9-12 Synthetic example

<Reaction Scheme 32>

After mixing the five-membered hetero compound (8.0g, 20mmol) and 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (9.3g, 24mmol) in toluene, Pd ₂ (dba) ₃ , After adding PPh ₃ and NaOt-Bu, respectively, the mixture was refluxed with stirring at 100° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 8.8g of product 9-12 (yield 62%).

( 10)Product 10-16 Synthetic example

<Reaction Scheme 33>

After mixing the five-membered hetero compound (6.9g, 20mmol) and 2-(4-bromophenyl)imidazo[1,2-a]pyridine (6.6g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , NaOt- After each addition of Bu, the mixture was refluxed with stirring at 100° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 6.9 g (yield 64%) of product 10-16.

( 11)Product 11-3 Synthetic example

<Scheme 34>

After mixing the five-membered hetero compound (7.5 g, 20 mmol) and 2-bromopyridine (3.8 g, 24 mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and then stirred at 100° C. for 24 hours. Let it reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 6.2g (yield 69%) of product 11-3.

( 12)Product 12-8 Synthetic example

<Scheme 35>

After mixing the five-membered hetero compound (7.5g, 20mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , NaOt After each addition of -Bu, the mixture was refluxed with stirring at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 7.7 g of product 12-8 (64% yield).

( 13)Product 13-1 Synthetic example

<Scheme 36>

After mixing the five-membered hetero compound (5.5g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and stirred and refluxed at 100°C for 24 hours . After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 4.8g (yield 67%).

( 14)Product 14-7 Synthetic example

<Scheme 37>

After mixing the five-membered hetero compound (12.7g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and stirred and refluxed at 100° C. for 24 hours. . After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 9.2g (yield 65%).

( 15)Product 15-9 Synthetic example

<Scheme 38>

After mixing the five-membered hetero compound (7.7g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and stirred and refluxed at 100° C. for 24 hours. . After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 6.1g (yield 67%).

( 16)Product 16-15 Synthetic example

<Scheme 39>

After mixing the five-membered hetero compound (8.0g, 20mmol) and the substituted pyridine compound (7.5g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and then at 100° C. for 24 hours. It was stirred and refluxed. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 7.9 g (yield 62%).

( 17)Product 17-11 Synthetic example

<Reaction Scheme 40>

After mixing the five-membered hetero compound (7.5g, 20mmol) and 5-bromo-2,4-diphenylpyrimidine (7.5g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively. The mixture was stirred and refluxed at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 7.6 g (yield 61%).

( 18)Product 18-14 Synthetic example

<Reaction Scheme 41>

After mixing the five-membered hetero compound (7.5g, 20mmol) and 4-(4-bromophenyl)-2,6-diphenylpyrimidine (9.3g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were respectively added. After the addition, the mixture was stirred and refluxed at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 8.7 g (yield 64%).

( 19)Product 19-2 Synthetic example

<Reaction Scheme 42>

After mixing the five-membered hetero compound (8.5g, 20mmol) and 2-bromonaphthalene (5.0g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added respectively, followed by stirring at 100° C. for 24 hours. Let it reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain product 7.7g (yield 71%).

( 20)Product 20-8 Synthetic example

<Scheme 43>

After mixing the five-membered hetero compound (8.5g, 20mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , NaOt After each addition of -Bu, the mixture was refluxed with stirring at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 8.7g (yield 67%).

( 21)Product 21-12 Synthetic example

<Reaction Scheme 44>

After mixing the five-membered hetero compound (8.0g, 20mmol) and 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (9.3g, 24mmol) in toluene, Pd ₂ (dba) ₃ , After adding PPh ₃ and NaOt-Bu, respectively, the mixture was refluxed with stirring at 100° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 8.8g (yield 62%).

( 22)Product 22-16 Synthetic example

<Scheme 45>

After mixing the five-membered hetero compound (6.9g, 20mmol) and 2-(4-bromophenyl)imidazo[1,2-a]pyridine (6.6g, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , NaOt- After each addition of Bu, the mixture was refluxed with stirring at 100° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain product 6.8g (yield 63%).

( 23)Product 23-3 Synthetic example

<Reaction Scheme 46>

After mixing the five-membered hetero compound (7.5 g, 20 mmol) and 2-bromopyridine (3.8 g, 24 mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added, respectively, and then stirred at 100° C. for 24 hours. Let it reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain product 6.2g (yield 69%).

( 24)Product 24-8 Synthetic example

<Reaction Scheme 47>

After mixing the five-membered hetero compound (7.5g, 20mmol) and 2-bromo-4-phenylquinazoline (7.5g, 24mmol) in toluene, after adding Pd ₂ (dba) ₃ , PPh ₃ , NaOt-Bu, respectively, 100℃ The mixture was refluxed with stirring for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and then the resulting organic material was silicagel column and recrystallized to obtain product 7.8g (yield 65%).

( 25)Product 25-1 Synthetic example

<Reaction Scheme 48>

After mixing the five-membered hetero compound (6.7g, 20mmol) and 2-bromo-4-phenylquinazoline (6.8g, 24mmol) in toluene, after adding Pd ₂ (dba) ₃ , PPh ₃ , NaOt-Bu, respectively, 100℃ The mixture was refluxed with stirring for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 6.6g (yield 61%).

( 26)Product 26-17 Synthetic example

<Reaction Scheme 49>

After mixing a 5-membered hetero compound (6.7g, 20mmol) and 3-(2-bromoquinazolin-4-yl)-9-phenyl-9H-carbazole (10.8, 24mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ , After each addition of NaOt-Bu, the mixture was refluxed with stirring at 100° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain product 8.2g (yield 58%).

FD-MS values for specific compounds of the present invention are shown in Table 4 below.

[Table 4]

Manufacturing evaluation of organic electric devices

[ Experimental Example 1] (Phosphorus Green Host)

The organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention obtained through synthesis as a light emitting host material of the light emitting layer.

First, N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl as a hole injection layer first on the ITO layer (anode) formed on the glass substrate. )-N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) After vacuum-depositing a film to form a hole injection layer with a thickness of 60 nm, 4,4-bis[ N -(1- -Naphthyl) -N -phenylamino]biphenyl (hereinafter abbreviated as NPD) was vacuum-deposited to a thickness of 20 nm to form a hole transport layer. Next, a compound of the present invention was doped with a host material on the hole transport layer, and Ir(ppy) ₃ [tris(2-phenylpyridine)-iridium] was doped with a 95:5 weight ratio as a dopant to deposit a light emitting layer with a thickness of 30 nm. Subsequently, (1,1'-bisphenyl)-4-oleito)bis(2-methyl-8-quinolineoleito)aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited on the light emitting layer to a thickness of 10 nm. A hole blocking layer was formed, and an electron transport layer was formed on the hole blocking layer with Tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) to a thickness of 40 nm. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

[ Comparative example One]

An organic electroluminescent device was manufactured in the same manner as in the above Experimental Example, except that the following Comparative Compound 2 was used instead of the compound of the present invention as a host material when forming the emission layer.

<Comparative Compound 1>

[ Comparative example 2]

An organic electroluminescent device was manufactured in the same manner as in the above Experimental Example, except that the following Comparative Compound 3 was used instead of the compound of the present invention as a host material when forming the emission layer.

<Comparative Compound 2>

[ Comparative example 3]

An organic electroluminescent device was manufactured in the same manner as in the above Experimental Example, except that the following Comparative Compound 3 was used instead of the compound of the present invention as a host material when forming the emission layer.

<Comparative Compound 3>

In the embodiment, prepared as examples and comparative examples the organic was applied with a forward bias DC voltage to the electroluminescent device Photo Research (photoresearch) 's were measured and electroluminescence (EL) properties by PR-650, from the measurement result 300cd / m ² based on the luminance The T90 life was measured using a life measurement equipment manufactured by Max Science.

Table 5 below shows device fabrication and evaluation results for Experimental Example 1 and Comparative Examples 1 to 3 to which the compound according to the invention was applied.

[Table 5]

As can be seen from the results of the above table, the present invention shows higher luminous efficiency and higher lifetime than Comparative Examples 1 to 3, and in particular, a relatively low driving voltage and higher efficiency and lifetime compared to Comparative Examples 2 and 3 Is shown. This is thought to increase the life of the core by making the HOMO of the core deeper by introducing a substituent to the backbone of the five-membered heterocyclic ring, and having a suitable HOMO value with HTL, thereby increasing the lifespan of the hole, and also the electron density of LUMO by the backbone substituent. It is judged to show high efficiency by delocalizing.

[ Experimental Example 2] (phosphorescence Red Host)

An organic electroluminescent device was manufactured according to a conventional method using the compound obtained through synthesis as a light emitting host material of the light emitting layer.

First, 2-TNATA was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a 60 nm thick hole injection layer, and then NPD was deposited on the hole injection layer to a thickness of 20 nm to form a hole transport layer. . Next, as a host on the hole transport layer, doped with a compound of the present invention, a dopant material (piq) ₂ Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] at a weight ratio of 95:5 to 30 nm thick A light emitting layer was deposited. Subsequently, a hole blocking layer was formed by vacuum-depositing BAlq to a thickness of 10 nm on the light emitting layer, and an electron transport layer of Alq3 was formed to a thickness of 440 nm on the hole blocking layer. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, a halogenated alkali metal, to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

In the embodiment, prepared as examples and comparative examples the organic was applied with a forward bias DC voltage to the electroluminescent device Photo Research (photoresearch) 's were measured and electroluminescence (EL) properties by PR-650, from the measurement result 300cd / m ² based on the luminance T95 life was measured by a life measurement equipment manufactured by Max Science.

Table 6 below shows device fabrication and evaluation results for Experimental Example 2 and Comparative Examples 4 to 5 to which the compound according to the invention was applied.

[Table 6]

As can be seen from the results of Table 6, the organic electroluminescent device using the material for an organic electroluminescent device of the present invention is used as a red light emitting layer material, it is possible to significantly improve the high luminous efficiency and life, color purity. In particular, when comparing the device results of Comparative Compound 2, Comparative Compound 3 and the compound of the present invention, a substituent is introduced into the five-membered heterocyclic backbone, and the compounds of the present invention to which quinazoline derivatives are connected exhibit higher efficiency and higher lifespan. Was confirmed.

It is apparent that the same effect can be obtained even when the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer.

The same effects can be obtained even when the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light-emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer.

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

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

Claims (8)

Compound represented by the formula (3):
<Formula 3>

In Chemical Formula 3,
X is C(R ₁₁ )(R ₁₂ ),
R ₁ to R ₁₀ are hydrogen independently of each other, R ₅ and R ₆ may combine with each other to form a ring, and R ₇ to R ₁₀ may combine with adjacent groups to form a benzene ring,
L is quinazoline,
Ar ₁ is a C ₆ ~ C ₁₆ aryl group; Or a heterocyclic group of C ₂ ~ C ₁₈ containing at least one heteroatom of O, N and S,
R ₁₁ and R ₁₂ are each independently a C ₁ ~ C ₁₀ alkyl group,
The aryl group and the heterocyclic group are each deuterium; C ₆ ~ C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; It may be substituted with one or more substituents selected from the group consisting of. According to claim 1,
Formula 3 is a compound characterized in that represented by one of the following formula:
<Formula 19><Formula22><Formula23>

In Chemical Formulas 19, 22 and 23, X, R ₅ to R ₁₀ , L, Ar ₁ are as defined in claim ₁ . According to claim 1,
The compound represented by Chemical Formula 3 is represented by the following Chemical Formula 20 or Chemical Formula 21:
<Formula 20><Formula21>

In Chemical Formula 20 and Chemical Formula 21, X, L, and Ar ₁ are as defined in claim ₁ . According to claim 1,
The compound represented by Chemical Formula 3 is one of the following compounds:

. In the organic electrical device including a first electrode, a second electrode and an organic material layer located between the first electrode and the second electrode,
The organic material layer is an organic electroluminescent device comprising the compound of any one of claims 1 to 4. The method of claim 5,
The organic material layer includes a light emitting layer, and the compound is an organic electric device characterized in that it is used as a host material of the light emitting layer. A display device comprising the organic electroluminescent element of claim 5; And
An electronic device comprising; a control unit for driving the display device. The method of claim 7,
The organic electroluminescent device is an electronic device characterized in that it is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a monochromatic or white lighting device.

Images