KR20210008323A - 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 an element, an organic electric element using the same, and an electronic device thereof. The present invention provides a compound represented by chemical formula 1. In another aspect, the present invention provides the organic electric element and the electronic device using the compound represented by the chemical formula.

Description

Compound for organic electric device, organic electric device using the same, and electronic device thereof {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 device, an organic electric device using the same, and an electronic device thereof.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emission phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered 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 electric device can 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, according to their functions.

On the other hand, it delays the penetration and diffusion of metal oxides from the anode electrode (ITO) into the organic layer, which is one of the causes of shortening the lifespan of organic electronic devices, and is stable against Joule heating, i. It is necessary to develop a material for a hole injection layer having a temperature. In addition, it is reported that the low glass transition temperature of the material for the hole transport layer has a great influence on the life of the device according to the characteristic that the uniformity of the thin film surface collapses when the device is driven. In addition, the deposition method is the mainstream in the formation of OLED devices, and a material that can withstand such a deposition method for a long time, that is, a material having strong heat resistance properties is required.

In order to fully exhibit the excellent characteristics of the above-described organic electronic device, materials that form the organic material layer in the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, etc., are supported by stable and efficient materials. Although this should be preceded, development of a stable and efficient organic material layer material for an organic electric device has not been sufficiently developed, and therefore, development of a new material is continuously required.

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

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 and an electronic device using the compound represented by the above formula.

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 diagram 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 elements of each drawing, it should be noted that the same elements are assigned the same numerals as possible even if they are indicated on different drawings. In addition, in describing the present invention, when it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, the detailed description thereof will be omitted.

In addition, in describing the constituent elements of the present invention, terms such as first, second, A, B, (a) and (b) may be used. These terms are only used to distinguish 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 or connected to that other component, but another component between each component It should be understood that elements may be “connected”, “coupled” or “connected”.

Meanwhile, the terms "halo" or "halogen" used in the present specification are

One includes fluorine, chlorine, bromine, and iodine.

The term "alkyl" or "alkyl group" as used herein has a carbon number of 1 to 60 unless otherwise specified, and is not limited thereto.

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

The term "cycloalkyl" as used in the present invention means an 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 a carbon number of 1 to 60 unless otherwise specified, and is not limited thereto.

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

In the present invention, an aryl group or an arylene group means 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, a biphenyl group, a fluorene group, or a spirofluorene group.

As used herein, the term “heteroalkyl” refers to an alkyl containing one or more heteroatoms unless otherwise specified. The term "heteroaryl group" or "heteroarylene group" as used herein refers to an aryl group or arylene group having 3 to 60 carbon atoms each including one or more heteroatoms, unless otherwise specified, and is limited thereto. No, it includes not only a single ring but also a heterocycle, and may be formed by combining adjacent groups.

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

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

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

Unless otherwise stated, the term “saturated or unsaturated ring” as used herein refers to 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 aforementioned hetero compounds include one or more heteroatoms, but are not limited thereto.

In addition, unless explicitly stated, the term "substituted or unsubstituted" used in the present invention means "substituted" deuterium, halogen, amino group, nitrile group, nitro group, C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ alkylamine group, C ₁ to C ₂₀ alkylthiophene group, C ₆ to C ₂₀ arylthiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C ₅ ~ C ₂₀ heterocyclic group, 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 a substrate 110. ) Between the organic material layer containing the compound represented by the 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 include a hole injection layer 130, a hole transport layer 140, an emission layer 150, an electron transport layer 160, and an electron injection layer 170 sequentially on the first electrode 120. In this case, other layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, a buffer layer 141, etc. may be further included, and the electron transport layer 160 may serve as a hole blocking layer.

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

The compound according to the present invention applied to the organic material layer is a material of a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, an electron injection layer 170, a host of the emission layer 150, a dopant, or a capping layer. 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 a 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, an electron transport layer ( After forming an organic material layer including 160) and the electron injection layer 170, it may be manufactured by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is made of a variety of polymeric materials, so that it is reduced by a solution process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. It can be made in a number of layers. 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 electric device according to the present invention may be a top emission type, a bottom emission type, or a double side 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 photoconductor (OPC), an organic transistor (organic TFT), and a single color or white lighting device.

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including 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 consoles, various TVs, and various computers.

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

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

[Formula 1]

In Formula 1,

R ₁ to R ₁₀ are ⅰ) independently of each other, hydrogen, deuterium, halogen, C ₆ to C ₆₀ aryl group, fluorenyl group, C ₃ to C ₆₀ aliphatic ring and C ₆ to C ₆₀ aromatic ring fusion A cyclic group, a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P, -LN(R')(R"), a C ₁ to C ₅₀ alkyl group, It may be selected from the group consisting of an alkenyl group of C ₂ to C ₂₀ , an alkoxy group of C ₁ to C _{30 and} an aryloxy group of C ₆ to C _30. However, when 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 Any one of at least one may not be hydrogen, and when Y is O, at least one of R ₁ to R ₄ and R ₇ to R ₁₀ may not be hydrogen.

Alternatively, they may form at least one ring by ii) bonding adjacent groups to each other, wherein the group not forming a ring is the same as defined in i).

Here,'neighboring groups combine with each other to form at least one ring' means that R ₁ and R ₂ are bonded to each other, R ₂ and R ₃ are bonded to each other, and/or R ₃ and R ₄ are bonded to each other to form at least one ring. It means to form a compound. At this time, since it is important that neighboring groups are bonded to each other to form a ring, the scope of the present invention is not limited by which substituents and through which reactions they are 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 bonding of adjacent groups among R ₁ to R ₁₀ may be a monocyclic or polycyclic aromatic ring or a hetero ring including at least one hetero atom, as well as a form in which an aromatic ring and an aliphatic ring are fused. For example, neighboring groups among R ₁ and R _{4 may} be bonded to each other to form an aromatic ring such as benzene, naphthalene, phenanthrene, and the like, and the number of nuclear carbon atoms of the aromatic ring formed at this time is preferably 6 to 60. For example, when R ₁ and R ₂ are bonded to each other to form a benzene ring, and R ₃ and R ₄ are bonded to each other to form a benzene ring, a phenanthrene form may be formed together with the benzene ring of the parent nucleus to which they are bonded.

In addition, neighboring groups among R ₁ to R _{10 may} be bonded to each other to form a heterocycle such as thiophene, furan, pyridine, indole, quinoline, and the like, wherein the number of nuclear carbons may be 2 to 60. In addition, in the case of a polycyclic ring, it may be a fused form or a form in which a plurality of rings are 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 equal to or greater than m+n=1, that is, when m is 1, n is 0, and when m is 0, n is 1. And here, R ₁₁ And R ₁₂ are independently of each other hydrogen, a C ₆ ~ C ₆₀ aryl group, a C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P, -LN(R ') (R") or may be a C ₁ ~ C ₅₀ alkyl group.

L is a direct bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; And a divalent aliphatic hydrocarbon group; it may be selected from the group consisting of. At this time, the arylene group, fluorenylene 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 refers to the absence of L, and referring to 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, C ₆ to C ₆₀ aryl group, C ₂ to C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si and P, flu It is selected from the group consisting of an orenyl group, a C ₁ to C ₅₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₃₀ alkoxyl group, and -N(R')(R”),

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

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

When the R ₁ to R ₁₂ , Ar ₁ , R'and R" are an aryl group, it is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ to C ₂₀ alkylthio group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, 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 an arylalkyl group and a C ₈ ~ C ₂₀ arylalkenyl group,

When the R ₁ to R ₁₂ , Ar ₁ , R'and R" are heterocyclic groups, which are deuterium, halogen, silane groups, cyano groups, nitro groups, C ₁ to C ₂₀ alkoxyl groups, 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 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 the R ₁ to R ₁₀ , Ar ₁ , R'and R" are fluorenyl groups, it is 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 the R ₁ ~ R _1O is fused when ring group, which come alkylthio of deuterium, a halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro _{group, C 1 ~ C 20, C} 1 ~ C 20 alkoxy Real group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group (alkynyl), C ₆ ~ C ₂₀ aryl group, C ₆ substituted with deuterium Of ~C ₂₀ aryl group, 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 an arylalkyl group and a C ₈ ~ C ₂₀ arylalkenyl group,

When the R ₁ to R ₁₂ is an alkyl group, it is a halogen, a silane group, a boron group, a cyano group, a C ₁ to C ₂₀ alkoxyl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group (alkenyl ), 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 the R ₁ to R ₁₀ is an alkenyl group, it is deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group (alkenyl ), 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 an arylalkyl group and a C ₈ ~ C ₂₀ arylalkenyl group.

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

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

Meanwhile, the compound represented by Formula 1 may be represented by the following Formula 2 or 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, Formula 1 may be represented by the following compounds.

Hereinafter, examples for synthesizing the compound represented by Formula 1 and an organic electric device according to the present invention will be described in detail, but the present invention is not limited to the following examples.

Synthesis example

Exemplarily, the compounds (final products) according to the present invention are prepared by reacting one of Sub 1 to Sub 22 with Sub 23 as shown in Scheme 1 below.

<Reaction Scheme 1>

[ Example One]

One. Sub Synthesis of 1

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

<Reaction Scheme 2>

(One) Sub 1-2 Synthesis example

After dissolving Sub 1-1 in a carbon disulfide solvent under nitrogen, 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 pressure reducing device, and the resulting product was recrystallized using an ethanol solvent to obtain the desired Sub 1-2.

(2) Sub 1-3 Synthesis 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 reactant 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 1-3.

(3) Sub 1-4 Synthesis example

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

(4) Sub One Synthesis example

The obtained Sub 1-4 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by 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.

<Reaction Scheme 3>

(One) Sub 2-2 Synthesis 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the resulting product was concentrated in an organic solvent to obtain a desired Sub 2-2 by column chromatography.

(2) Sub 2-3 Synthesis example

Sub 2-2 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ substituted with R ₁ ~R ₄ were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the resulting product was concentrated with an organic solvent to obtain a desired Sub 2-3 by column chromatography.

(3) Sub 2 Synthesis example

Sub 2-3 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the 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 can be synthesized by the reaction route of Scheme 4 below.

<Reaction Scheme 4>

(One) Sub 3-1 Synthesis example

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

(2) Sub 3-2 Synthesis example

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

(3) Sub 3-3 Synthesis example

The obtained Sub 3-2 and trifluoromethanesulfonic acid were added, stirred at room temperature for 24 hours, then water and pyridine (8:1) (pyridine (8:1)) were slowly added and refluxed for 30 minutes. Lower the temperature, extract with CH ₂ Cl ₂ and wash with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 3-3.

(4) Sub 3-4 Synthesis example

The obtained Sub 3-3 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ substituted with R _{1 to 4} were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 3-4.

(5) Sub 3 Synthesis example

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

[ Example 4]

One. Sub 4 synthesis

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

<Reaction Scheme 5>

(One) Sub 4-1 Synthesis example

Dissolve 5-bromobenzo[b]naphtho[2,1-d]thiophene substituted with R _{7 ~10} in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly add n-BuLi (2.5 M inhexane) 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 4-1.

(2) Sub 4-2 Synthesis example

The obtained Sub 4-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ substituted with R _{1 to 4} were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 4-2.

(3) Sub 4 Synthesis example

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

[ Example 5]

One. Sub 5 synthesis

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

<Reaction Scheme 6>

(One) Sub 5-1 Synthesis example

Dissolve 5-bromobenzo[b]naphtho[2,1-d]thiophene in anhydrous THF, lower the temperature of the reactant to -78 °C, add n-BuLi (2.5 M inhexane) slowly dropwise, and then add the reactant to 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 5-1.

(2) Sub 5-2 Synthesis example

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

(3) Sub 5 Synthesis example

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

[ Example 6]

One. Sub 6 synthesis

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

<Reaction Scheme 7>

(One) Sub 6-1 Synthesis example

After dissolving 5-bromobenzo[d]naphtho[2,1-b]thiophene, 1-bromo-2-nitronaphthalene, Pd(PPh ₃ ) ₄ and 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 reaction product was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 6-1.

(2) Sub 6 Synthesis example

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

[ Example 7]

One. Sub 7 synthesis

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

<Reaction Scheme 8>

(One) Sub 7-1 Synthesis example

Dissolve 5-bromobenzo[b]naphtho[2,1-d]thiophene in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly add n-BuLi (2.5 M inhexane) dropwise, and then add the reactant to 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 7-1.

( 2)Sub 7-2 Synthesis example

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

( 3)Sub 7 Synthesis example

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

[ Example 8]

One. Sub 8 synthesis

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

<Reaction Scheme 9>

(One) Sub 8-1 Synthesis example

Dissolve 5-bromobenzo[d]naphtho[2,1-b]thiophene in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly add n-BuLi (2.5 M inhexane) dropwise, then add the reactant to 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 8-1.

( 2)Sub 8-2 Synthesis example

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

( 3)Sub 8 Synthesis example

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

[ Example 9]

One. Sub 9 synthesis

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

<Reaction Scheme 10>

( 1)Sub 9-1 Synthesis example

2-bromodibenzo[b,d]thiophene substituted with R _{5 ~6} is dissolved in anhydrous THF, the temperature of the reactant is lowered to -78 °C, n-BuLi (2.5 M inhexane) is slowly added dropwise, and the reactant is 0 It was stirred at °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78 °C, trimethyl borate was added dropwise, and then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 9-1.

( 2)Sub 9-2 Synthesis example

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

( 3)Sub 9 Synthesis example

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

[ Example 10]

One. Sub 10 synthesis

Sub 10 can be synthesized by the reaction route of Scheme 11.

<Reaction Scheme 11>

( 1)Sub 10-1 Synthesis example

3-bromodibenzo[b,d]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reaction mixture was lowered to -78 ℃, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction product was 0 It was stirred at °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78 °C, trimethyl borate was added dropwise, and then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 10-1.

( 2)Sub 10-2 Synthesis example

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

( 3)Sub 10 Synthesis example

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

[ Example 11]

One. Sub 11 synthesis

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

<Reaction Scheme 12>

( 1)Sub 11-1 Synthesis example

2-bromodibenzo[b,d]thiophene substituted with R _{5 ~6} is dissolved in anhydrous THF, the temperature of the reactant is lowered to -78 °C, n-BuLi (2.5 M inhexane) is slowly added dropwise, and the reactant is 0 It was stirred at °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78 °C, trimethyl borate was added dropwise, and then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 11-1.

( 2)Sub 11-2 Synthesis example

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

( 3)Sub 11 Synthesis example

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

[ Example 12]

One. Sub 12 synthesis

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

<Reaction Scheme 13>

( 1)Sub 12-1 Synthesis example

3-bromodibenzo[b,d]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reaction mixture was lowered to -78 ℃, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction product was 0 It was stirred at °C for 1 hour. Thereafter, the temperature of the reactant was lowered to -78 °C, trimethyl borate was added dropwise, and then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 12-1.

( 2)Sub 12-2 Synthesis example

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

( 3)Sub 12 Synthesis example

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

[ Example 13]

One. Sub 13 synthesis

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

<Reaction Scheme 14>

( 1)Sub 13-1 Synthesis example

Dissolve 5-bromodinaphtho[1,2-b:2',1'-d]thiophene in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly add n-BuLi (2.5 M inhexane) 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 13-1.

( 2)Sub 13-2 Synthesis example

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

( 3)Sub 13 Synthesis example

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

[ Example 14]

One. Sub 14 synthesis

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

<Reaction Scheme 15>

( 1)Sub 14-1 Synthesis example

Dissolve 5-bromodinaphtho[2,1-b:1',2'-d]thiophene in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly add n-BuLi (2.5 M inhexane) 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 14-1.

( 2)Sub 14-2 Synthesis example

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

( 3)Sub 14 Synthesis example

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

[ Example 15]

One. Sub 15 synthesis

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

<Reaction Scheme 16>

( 1)Sub 15-1 Synthesis example

14-bromonaphtho[2,1-d]phenanthro[9,10-b]thiophene was dissolved in anhydrous THF, the temperature of the reaction mixture was lowered to -78 ℃, 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 then stirred at room temperature for 12 hours. When the reaction was completed, an aqueous 2N-HCl solution was added, stirred for 30 minutes, and extracted with ether. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 15-1.

( 2)Sub 15-2 Synthesis example

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

( 3)Sub 15 Synthesis example

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

[ Example 16]

One. Sub 16 synthesis

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

<Scheme 17>

( 1)Sub 16-1 Synthesis example

Dissolve 5-bromonaphtho[2,1-b]phenanthro[9,10-d]thiophene in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly add n-BuLi (2.5 M inhexane) 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 16-1.

( 2)Sub 16-2 Synthesis example

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

( 3)Sub 16 Synthesis example

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

[ Example 17]

One. Sub 17 synthesis

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

<Reaction Scheme 18>

( 1)Sub 17-1 Synthesis 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 °C, and slowly add n-BuLi (2.5 M inhexane) 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 17-1.

( 2)Sub 17-2 Synthesis example

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

( 3)Sub 17 Synthesis example

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

[ Example 18]

One. Sub 18 synthesis

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

<Reaction Scheme 19>

( 1)Sub 18-1 Synthesis example

Dissolve 9-bromobenzo[b]naphtho[1,2-d]thiophene substituted with R _{5 ~6} in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly add n-BuLi (2.5 M inhexane) 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 18-1.

( 2)Sub 18-2 Synthesis example

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

( 3)Sub 18 Synthesis example

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

[ Example 19]

One. Sub 19 synthesis

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

<Reaction Scheme 20>

( 1)Sub 19-1 Synthesis example

12-bromobenzo[d]phenanthro[9,10-b]thiophene substituted with R _{5 ~6} was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ℃, 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 then stirred at room temperature for 12 hours. When the reaction was completed, an aqueous 2N-HCl solution was added, stirred for 30 minutes, and extracted with ether. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 19-1.

( 2)Sub 19-2 Synthesis example

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

( 3)Sub 19 Synthesis example

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

[ Example 20]

One. Sub 20 synthesis

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

<Reaction Scheme 21>

( 1)Sub 20-1 Synthesis example

Dissolve 11-bromobenzo[b]phenanthro[9,10-d]thiophene substituted with R _{5 ~6} in anhydrous THF, lower the temperature of the reactant to -78 °C, and slowly add n-BuLi (2.5 M inhexane) 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 20-1.

( 2)Sub 20-2 Synthesis example

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

( 3)Sub 20 Synthesis example

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

[ Example 21]

One. Sub 21 synthesis

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

<Reaction Scheme 22>

( 1)Sub 21-2 Synthesis example

Sub 21-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ , K ₂ CO ₃ substituted with R _{1 to 4} were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 21-2.

( 2)Sub 21 Synthesis example

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

[ Example 22]

One. Sub 22 synthesis

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

<Reaction Scheme 23>

( 1)Sub 22-1 Synthesis 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 add 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 then 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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 22-1.

( 2)Sub 22-2 Synthesis example

The obtained Sub 22-1 and 1-bromo-2-nitrobenzene, Pd(PPh ₃ ) ₄ and K ₂ CO ₃ substituted with R _{1 to 4} were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 22-2.

( 3)Sub 22 Synthesis example

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

[ Example 23]

Sub 23 examples

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 Synthesis example

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

(One) Product 1-1 Synthesis example

<Reaction Scheme 24>

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

( 2)Product 2-6 Synthesis example

<Reaction Scheme 25>

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

( 3)Product 3-9 Synthesis example

<Scheme 26>

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

( 4)Product 4-15 Synthesis 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 , NaOt-Bu were added, respectively, at 100° C. for 24 hours Stir to reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 7.9 g (yield 63%) of product 4-15.

( 5)Product 5-11 Synthesis example

<Reaction Scheme 28>

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

( 6)Product 6-14 Synthesis example

<Reaction Scheme 29>

Five-atom hetero compounds (7.5g, 20mmol) and 4-(4-bromophenyl)-2,6-diphenylpyrimidine (9.3g, 24mmol) were mixed in toluene and then Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were respectively After 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 recrystallized with a silicagel column to obtain 8.8 g (yield 65%) of product 6-14.

( 7)Product 7-2 Synthesis example

<Reaction 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 Reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 7.7 g (yield 70%) of product 7-2.

( 8)Product 8-8 Synthesis example

<Reaction Scheme 31>

Five-membered hetero compounds (8.5g, 20mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) were mixed in toluene and then Pd ₂ (dba) ₃ , PPh ₃ , NaOt After each -Bu was added, 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 recrystallized with a silicagel column to obtain 8.6 g (yield 66%) of product 8-8.

( 9)Product 9-12 Synthesis example

<Reaction Scheme 32>

After mixing a 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 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 recrystallized with a silicagel column to obtain 8.8 g (62% yield) of product 9-12.

( 10)Product 10-16 Synthesis example

<Reaction Scheme 33>

After mixing a 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 stirred and refluxed at 100°C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 6.9 g (yield 64%) of product 10-16.

( 11)Product 11-3 Synthesis example

<Reaction Scheme 34>

Five-atom hetero compounds (7.5g, 20mmol) and 2-bromopyridine (3.8g, 24mmol) were mixed in toluene, and then Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added respectively, followed by stirring at 100° C. for 24 hours Reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 6.2 g (yield 69%) of product 11-3.

( 12)Product 12-8 Synthesis example

<Reaction Scheme 35>

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

( 13)Product 13-1 Synthesis example

<Reaction Scheme 36>

After mixing the five-membered hetero compound (5.5g, 20mmol) and bromobenzene (3.8g, 24mmol) in toluene, add Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu respectively, and then stir and reflux 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 recrystallized with a silicagel column to obtain 4.8 g (yield 67%) of a product.

( 14)Product 14-7 Synthesis example

<Scheme 37>

Five-membered hetero compounds (12.7g, 20mmol) and bromobenzene (3.8g, 24mmol) are mixed in toluene, then Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu are added, respectively, and then 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 recrystallized with a silicagel column to give a product 9.2g (yield 65%).

( 15)Product 15-9 Synthesis example

<Scheme 38>

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

( 16)Product 16-15 Synthesis example

<Reaction 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 , NaOt-Bu were added, respectively, at 100° C. for 24 hours Stir to reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain a product of 7.9 g (62% yield).

( 17)Product 17-11 Synthesis example

<Reaction Scheme 40>

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

( 18)Product 18-14 Synthesis example

<Reaction Scheme 41>

Five-atom hetero compounds (7.5g, 20mmol) and 4-(4-bromophenyl)-2,6-diphenylpyrimidine (9.3g, 24mmol) were mixed in toluene and then Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were respectively After 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 recrystallized with a silicagel column to obtain a product 8.7 g (64% yield).

( 19)Product 19-2 Synthesis example

<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 Reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain a product of 7.7 g (yield 71%).

( 20)Product 20-8 Synthesis example

<Reaction Scheme 43>

Five-membered hetero compounds (8.5g, 20mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol) were mixed in toluene and then Pd ₂ (dba) ₃ , PPh ₃ , NaOt After each -Bu was added, 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 recrystallized with a silicagel column to obtain a product 8.7g (yield 67%).

( 21)Product 21-12 Synthesis example

<Reaction Scheme 44>

After mixing a 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 stirred and refluxed at 100° C. for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to give a product 8.8 g (62% yield).

( 22)Product 22-16 Synthesis example

<Scheme 45>

After mixing a 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 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 recrystallized with a silicagel column to obtain a product of 6.8 g (yield 63%).

( 23)Product 23-3 Synthesis example

<Scheme 46>

Five-atom hetero compounds (7.5g, 20mmol) and 2-bromopyridine (3.8g, 24mmol) were mixed in toluene, and then Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added respectively, followed by stirring at 100° C. for 24 hours Reflux. After extraction with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 6.2 g (yield 69%) of a product.

( 24)Product 24-8 Synthesis example

<Reaction Scheme 47>

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

( 25)Product 25-1 Synthesis example

<Scheme 48>

Five-atom hetero compounds (6.7g, 20mmol) and 2-bromo-4-phenylquinazoline (6.8g, 24mmol) were mixed in toluene, and then Pd ₂ (dba) ₃ , PPh ₃ , NaOt-Bu were added respectively, and then 100℃ The mixture was stirred at reflux for 24 hours. After extraction with ether and water, the organic layer was dried with MgSO ₄ and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain a product 6.6g (yield 61%).

( 26)Product 26-17 Synthesis example

<Reaction Scheme 49>

After mixing a five-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 NaOt-Bu was added, 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 recrystallized with a silicagel column to obtain 8.2 g (yield 58%) of the product.

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] (phosphorescent green host)

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

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

[ Comparative example One]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example except that Comparative Compound 2 below 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 Experimental Example, except that Comparative Compound 3 below 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 Experimental Example, except that Comparative Compound 3 below was used instead of the compound of the present invention as a host material when forming the emission layer.

<Comparative compound 3>

The electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch company by applying a forward bias DC voltage to the organic electroluminescent devices of the Examples and Comparative Examples thus prepared, and the measurement result was at 300 cd/m ² standard luminance. The T90 life was measured using a life measurement equipment manufactured by McScience.

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 exhibits higher luminous efficiency and higher lifetime than Comparative Examples 1 to 3, and in particular, compared to Comparative Examples 2 and 3, relatively low driving voltage and high efficiency and lifetime Represents. It is judged that the HOMO of the core becomes deeper by introducing a substituent into the five-atomic heterocyclic backbone, and it has an appropriate HOMO value with HTL, which increases the lifespan by increasing hole mobility. Also, the electron density of LUMO due to the substituent of the backbone It is judged to show high efficiency by becoming non-localized.

[ Experimental example 2] (phosphorescence Red Host)

The compound obtained through the synthesis was used as a light emitting host material for the light emitting layer to fabricate an organic light emitting device according to a conventional method.

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

The electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch company by applying a forward bias DC voltage to the organic electroluminescent devices of the Examples and Comparative Examples thus prepared, and the measurement result was at 300 cd/m ² standard luminance. The T95 life was measured through a life measurement equipment manufactured by McScience.

Table 6 below shows device fabrication and evaluation results for Experimental Examples 2 and 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, so that high luminous efficiency, lifespan, and color purity can be remarkably improved. In particular, when comparing the device results of Comparative Compound 2 and Comparative Compound 3 and the compound of the present invention, the compound of the present invention in which a substituent is introduced into the five-atomic heterocyclic backbone and the quinazoline derivatives are connected shows higher efficiency and higher lifespan. Confirmed.

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

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

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification 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 construed as being included in the scope of the present invention.

100: organic electric device 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 following formula (1):
<Formula 1>

In the above formula,
X and Y are independently of each other S or O,
m and n are each 0 or 1, m+n is 1,
R ₁ to R ₁₀ are each independently hydrogen or an aryl group of C ₆ to C ₂₀ , and when m is 1, neighboring R ₁ and R ₂ , neighboring R ₂ and R ₃ , neighboring R ₃ and R ₄ , Neighboring R ₇ and R ₈ , neighboring R ₈ and R ₉ , neighboring R ₉ and R ₁₀ at least one pair may be bonded to each other to form a benzene ring, provided that i) R ₁ to R ₄ , R Except when ₇ to R ₁₀ are all hydrogen, ii) when n is 1, R ₇ is hydrogen,
L is a single bond; Or O, N, S, Si and P is a C ₂ ~ C ₂₀ heterocyclic group containing at least one heteroatom,
Ar ₁ is a C ₆ ~ C ₂₀ aryl group; Or O, N, S, Si and P is a heterocyclic group of C ₂ ~ C ₂₀ containing at least one heteroatom, provided that, provided that, when m is 1 and L is a single bond, Ar ₁ is a heterocyclic group Is,
Said aryl groups and heterocyclic groups are each deuterium, a halogen, a silane group, a cyano group, an alkyl group of a nitro group, C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ of, C ₂ - a C ₂₀ alkenyl group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, and O, N, S, C ₂ containing at least one hetero atom of Si and P It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group of ~ C ₂₀ , provided that the aryl group substituted with a heterocyclic group in R ₂ is excluded. The method of claim 1,
Formula 1 is a compound represented by the following Formula 2 or Formula 3:
<Formula 2><Formula3>

In Formulas 2 and 3, R ₁ to R ₁₀ , X, Y, L, and Ar ₁ are the same as defined in claim ₁ . The method of claim 1,
Formula 1 is a compound represented by one of the following formulas:
<Formula 4><Formula5><Formula12><Formula13>

In the above formula, R ₅ , R ₆ , Y, L, Ar ₁ are the same as defined in claim ₁ . The method of claim 1,
The compound represented by Formula 1 is a compound characterized in that one of the following compounds:

. In the organic electric device comprising a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode,
An organic electric device characterized in that the organic material layer contains the compound of any one of claims 1 to 4. The method of claim 5,
The organic material layer includes an emission layer, and the compound is used as a host material for the emission layer. A display device comprising the organic electric device of claim 5; And
Electronic device including; a control unit for driving the display device. The method of claim 7,
The organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a single color or white lighting device.

Images