KR102170951B1 - 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 including a five-membered heterocycle capable of improving luminous efficiency, stability, and lifetime of the device, an organic electronic device using the same, and an electronic device thereof.

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 electronic 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 an organic material layer in an 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 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.e., high glass transition when the device is driven. There is a need 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 organic electronic device described above, 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.
2 shows a chemical formula according to an aspect of 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, if it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a 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 term "halo" or "halogen" used herein includes fluorine, chlorine, bromine, and iodine unless otherwise specified.

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, unless otherwise specified.

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 polymer materials, so that less 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 driving 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 the above formula,

R ₁ to R ₄ and R ₇ to R ₁₀ are i) independently of each other, hydrogen, deuterium, halogen, aryl group of C ₆ to C ₆₀ , fluorenyl group, aliphatic ring of C ₃ to C ₆₀ and C ₆ to C A fused ring group of an aromatic ring of ₆₀ , a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom of 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 C ₆ ~ C ₃₀ selected from the group consisting of aryloxy group, or ii) adjacent groups are bonded to each other at least Forms a single ring (in this case, the group that does not form a ring is the same as defined in i))

However, R ₁ ~ R _4, when the work both hydrogen R ₇ ~ R _10, at least one is not hydrogen, R ₇ ~ if R ₁₀ is one both hydrogen R ₁ ~ R ₄ at least one is not hydrogen. That is, the case where R ₁ to R ₁₀ are both hydrogen is excluded.

In addition, in ii), that neighboring groups among R ₁ to R ₄ and R ₇ to R ₁₀ are bonded to each other to form at least one ring, R ₁ and R _{2 together} , R ₂ and R _{3 together} , R ₃ and R _{4 together} , R ₇ and R _{8 together} , R ₈ and R _{9 together,} and/or R ₉ and R ₁₀ together to form a ring. 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 ₄ and R ₇ to R ₁₀ may be a monocyclic or polycyclic aromatic ring or a hetero ring containing at least one hetero atom, as well as a fusion of an aromatic ring and an aliphatic ring It may be in the form For example, neighboring groups among R ₁ and R _{10 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 ₇ and R ₈ are bonded to each other to form a benzene ring, and R ₉ and R ₁₀ 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 ₄ and R ₇ 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 carbons may be 2 to 60 days. have. 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.

On the other hand, R ₅ and R ₆ are independently of each other, hydrogen, deuterium, halogen, C ₆ ~ C ₆₀ aryl group, fluorenyl group, fusion of C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring 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 .

In the above formula, X and Y are each independently S, O or -Si(R ₁₁ )(R ₁₂ ). Here, R ₁₁ and R ₁₂ are independently of each other hydrogen, C ₆ ~ C ₆₀ of C ₂ ~ C ₆₀ containing at least one heteroatom of aryl group, fluorenyl group, O, N, S, Si and P It may be a heterocyclic group, or a C ₁ ~ C50 alkyl group. Meanwhile, each of m and n may be 0 or 1, but the case where both m and n are 0 is excluded. That is, since m+n=1 or more must be an integer, at least one of X and Y must exist.

L is a single 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; is selected from the group consisting of. At this time, groups excluding single bonds are nitro group, cyano group, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₁ ~ C ₂₀ alkoxy It may be substituted with one or more substituents selected from the group consisting of a group and an amino group.

In addition, Ar ₁ is a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P, an aryl group of C ₆ to C ₆₀ , a fluorenyl group, or -N(R ')(R”),

The R'and R" are independently of each other O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ heterocyclic group, C ₆ ~ C ₆₀ aryl group or fluorenyl group to be.

On the other hand, when the R ₁ to R ₁₀ , Ar ₁ , R', R", R ₁₁ and R ₁₂ are aryl groups, it is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ - of C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, C ₆ ~ C ₂₀ of the 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 ₁₀ , Ar ₁ , R', R", R ₁₁ and R ₁₂ are heterocyclic groups, it is deuterium, halogen, silane group, cyano group, nitro group, C ₁ to C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkenyl in the alkyl group, C ₂ ~ C ₂₀ of the diary, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₂ ~ C ₂₀ heterocyclic group, C of ₃ to C ₂₀ cycloalkyl group, C ₇ to 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 ₁₀ , Ar ₁ , R', R", R ₁₁ and R ₁₂ are fluorenyl groups, it is deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkyl group, C ₂ to for C ₂₀ alkenyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, from the group consisting of a cycloalkyl group of C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ of May be substituted with one or more selected substituents,

Wherein R ₁ ~ R _1O When the fused ring group, which is heavy hydrogen, a halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro group, C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ alkoxy group of C ₂₀ , an aryl group of C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the alkynyl group, a C ₆ ~ C ₂₀ substituted with an aryl group, a heavy hydrogen of C ₆ ~ C ₂₀ of, C ₂ to C ₂₀ heterocyclic group, C ₃ to C ₂₀ cycloalkyl group, C ₇ to 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, C of 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 an arylalkyl group and a C ₈ ~ C ₂₀ arylalkenyl group,

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, C of 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,

When the R ₁ to R ₁₀ is an alkoxyl group, it is deuterium, a 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 group substituted with deuterium, It may be substituted with one or more substituents selected from the group consisting of a C ₂ ~ C ₂₀ 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.

Formula 1 may be represented by Formula 2 below when n=0, and Formula 3 below when m=0.

<Formula 2> <Formula 3>

,

,

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

In addition, in Formula 2, when R ₁ to R ₄ are all hydrogen, as shown in Formula 2 below, R ₁ and R ₂ combine to form a benzene ring, and when R ₃ and R ₄ are hydrogen, the following Formula 5 As shown in the above, when R ₁ and R ₂ are hydrogen and R ₃ and R ₄ are bonded to each other to form a benzene ring, as shown in the following Formula 6, R ₁ and R ₂ are bonded to each other to form a benzene ring and at the same time R ₃ When and R ₄ are bonded to each other to form a benzene ring, it may be represented by the following formula (7).

In addition, in Formula 2, when all of R ₇ to R ₁₀ are hydrogen, as shown in Formula 8 below, R ₇ and R ₈ bond to each other to form a benzene ring, and when R ₉ and R ₁₀ are hydrogen, the following Formula 9 As such, when R ₁ and R ₂ are hydrogen and R ₃ and R ₄ are bonded to each other to form a benzene ring, R ₇ and R ₈ are bonded to each other to form a benzene ring, as shown in Formula 10 below, and R ₉ and When R ₁₀ is bonded to each other to form a benzene ring, it may be represented by the following formula (11).

Similarly, Formula 3 may be represented by one of the following formulas.

More specifically, the formulas may be one of the following compounds.

Hereinafter, a synthesis example of the compound of the present invention represented by the above formula and an example of manufacturing an organic electric device will be described in detail with examples, but the present invention is not limited to the following examples.

Synthesis example

Illustratively, the compound according to the present invention may be prepared by the following Synthesis Examples 1 or 2, and when neighboring groups among R ₁ to R ₄ and R ₇ to R ₁₀ are bonded to each other to form a ring, the following Synthesis Example It could be made by 3 or 4, etc. At this time, the ring is another known reaction (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.).

<Synthesis Example 1>

<Synthesis Example 2>

<Synthesis Example 3>

<Synthesis Example 4>

More specifically, the compound of the present invention can be prepared by the following Scheme 1.

Examples of product synthesis

The compound (final product) according to the present invention can be prepared by reacting one of Sub 1 to Sub 14 with Sub 15 as shown in Scheme 1 below.

<Reaction Scheme 1>

The starting materials (Sub 1 to Sub 14 materials, etc.) may be prepared by the following reaction formula, but may also be prepared by Synthesis Example 1 and Synthesis Example 2 as already described. Therefore, the preparation of the Sub material described below is only a synthesis example, and the scope of the present invention is not limited by these synthesis examples.

1-1. Example of Sub 1 synthesis method (when X or Y is S)

<Reaction Scheme 2>

(1) Sub1-1 synthesis method

The synthesized intermediate A and 2-bromocarbazole, Ph(PPh ₃ ), NaCO ₃ substituted with R ₁ to 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. 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 Sub1-1.

(2) Sub 1 synthesis method

Sub 1-1 was dissolved in trifluoromethanesulfonic acid solvent, and stirred at room temperature for 48 hours. When the reaction was completed, the reaction product was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed. 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 1.

1-2. Example of Sub 1'synthesis method (when X or Y is O)

<Reaction Scheme 3>

delete

(1) Sub 1-2 synthesis

After dissolving 3-bromodibenzo[b,d]furan (1 equivalent) in DMF, bispinacolatodiboron (1.1 equivalent), Pd (dppf)Cl ₂ catalyst (0.03 equivalent), KOAc (3 equivalent) are added in order After the mixture was stirred for 24 hours to synthesize a borate compound, the obtained compound was separated over a silicagel column and recrystallized to obtain Sub 1-2.

(2) Sub 1-3 synthesis

The obtained Sub 1-2 (1 equivalent) and 1-bromo-2-nitrobenzene (1 equivalent) substituted with R _{1 to 4} , Pd(PPh ₃ ) ₄ (0.03 equivalent), and K ₂ CO ₃ (3 equivalent) are anhydrous. After dissolving in THF and a small amount of water, it was 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 1-3.

(3) Sub 1'Synthesis Example

The obtained Sub 1-3 (1 equivalent) and triphenylphosphine (2.5 equivalents) 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 and Sub 1'are as follows, but are not limited thereto, and their FD-MS values are shown in Table 1.

compound FD-MS compound FD-MS Sub 1-(1) m/z=277.09 (C ₁₈ H ₇ D ₄ NS=277.38) Sub 1-(2) m/z=333.12 (C ₂₄ H ₁₅ NO=333.38) Sub 1-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 1-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 1-(5) m/z=425.12 (C ₃₀ H ₁₉ NS=425.54) Sub 1-(6) m/z=379.10 (C ₂₅ H ₁₇ NOS=379.47) Sub 1-(7) m/z=350.09 (C ₂₈ H ₁₄ N ₂ S=350.44) Sub 1-(8) m/z=465.16 (C ₃₃ H ₂₃ NS=465.61) Sub 1-(9) m/z=329.12 (C ₂₂ H ₁₉ NS=329.46) Sub 1-(10) m/z=632.23 (C ₄₅ H ₃₂ N ₂ S=632.81) Sub 1-(11) m/z=756.26 (C ₅₅ H ₃₆ N ₂ S=756.98) Sub 1-(12) m/z=754.24 (C ₅₅ H ₃₄ N ₂ S=754.94) Sub 1-(13) m/z=277.09 (C ₁₈ H ₇ D ₄ NS=277.38) Sub 1-(14) m/z=333.12 (C ₂₄ H ₁₅ NO=333.38) Sub 1-(15) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 1-(16) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 1-(17) m/z=425.12 (C ₃₀ H ₁₉ NS=425.54) Sub 1-(18) m/z=379.10 (C ₂₅ H ₁₇ NOS=379.47) Sub 1-(19) m/z=350.09 (C ₂₈ H ₁₄ N ₂ S=350.44) Sub 1-(20) m/z=465.16 (C ₃₃ H ₂₃ NS=465.61) Sub 1-(21) m/z=329.12 (C ₂₂ H ₁₉ NS=329.46) Sub 1-(22) m/z=632.23 (C ₄₅ H ₃₂ N ₂ S=632.81) Sub 1-(23) m/z=756.26 (C ₅₅ H ₃₆ N ₂ S=756.98) Sub 1-(24) m/z=754.24 (C ₅₅ H ₃₄ N ₂ S=754.94) Sub 1-(25) m/z=281.11 (C ₁₈ H ₃ D ₈ NS=399.51) Sub 1-(26) m/z=353.12 (C ₂₄ H ₁₁ D ₄ NS=353.47) Sub 1-(27) m/z=403.13 (C ₂₈ H1 ₃ D ₄ NS=403.53) Sub 1-(28) m/z=403.53 (C ₂₈ H ₁₃ D ₄ NS=403.53) Sub 1-(29) m/z=429.15 (C ₃₀ H ₁₅ D ₄ NS=429.57) Sub 1-(30) m/z=367.15 (C ₂₅ H ₁₃ D ₄ NO ₂ =367.43) Sub 1-(31) m/z=354.11 (C ₂₃ H ₁₀ D ₄ N ₂ S=354.46) Sub 1-(32) m/z=425.12 (C ₃₀ H ₁₉ NS=425.54) Sub 1-(33) m/z=389.18 (C ₂₈ H ₂₃ NO=389.49) Sub 1-(34) m/z=708.26 (C ₅₁ H ₃₆ N ₂ S=708.91) Sub 1-(35) m/z=832.29 (C ₆₁ H ₄₀ N ₂ S=833.05) Sub 1-(36) m/z=830.28 (C ₆₁ H ₃₈ N ₂ S=831.03)

2. Example of Sub 2 synthesis method <Scheme 4>

(1) Sub 2-2 synthesis method

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 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 the resulting product was concentrated in an organic solvent to obtain a desired Sub 2-2 by column chromatography.

(2) Sub 2-3 synthesis method

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 method

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.

compound FD-MS compound FD-MS Sub 2-(1) m/z=277.09 (C ₁₈ H ₇ D ₄ NS=277.38) Sub 2-(2) m/z=333.12 (C ₂₄ H ₁₅ NO=333.38) Sub 2-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 2-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 2-(5) m/z=425.12 (C ₃₀ H ₁₉ NS=425.54) Sub 2-(6) m/z=379.10 (C ₂₅ H ₁₇ NOS=379.47) Sub 2-(7) m/z=350.09 (C ₂₈ H ₁₄ N ₂ S=350.44) Sub 2-(8) m/z=465.16 (C ₃₃ H ₂₃ NS=465.61) Sub 2-(9) m/z=329.12 (C ₂₂ H ₁₉ NS=329.46) Sub 2-(10) m/z=632.23 (C ₄₅ H ₃₂ N ₂ S=632.81) Sub 2-(11) m/z=756.26 (C ₅₅ H ₃₆ N ₂ S=756.98) Sub 2-(12) m/z=754.24 (C ₅₅ H ₃₄ N ₂ S=754.94) Sub 2-(13) m/z=277.09 (C ₁₈ H ₇ D ₄ NS=277.38) Sub 2-(14) m/z=333.12 (C ₂₄ H ₁₅ NO=333.38) Sub 2-(15) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 2-(16) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 2-(17) m/z=425.12 (C ₃₀ H ₁₉ NS=425.54) Sub 2-(18) m/z=379.10 (C ₂₅ H ₁₇ NOS=379.47) Sub 2-(19) m/z=350.09 (C ₂₈ H ₁₄ N ₂ S=350.44) Sub 2-(20) m/z=465.16 (C ₃₃ H ₂₃ NS=465.61) Sub 2-(21) m/z=329.12 (C ₂₂ H ₁₉ NS=329.46) Sub 2-(22) m/z=632.23 (C ₄₅ H ₃₂ N ₂ S=632.81) Sub 2-(23) m/z=756.26 (C ₅₅ H ₃₆ N ₂ S=756.98) Sub 2-(24) m/z=754.24 (C ₅₅ H ₃₄ N ₂ S=754.94) Sub 2-(25) m/z=281.11 (C ₁₈ H ₃ D ₈ NS=399.51) Sub 2-(26) m/z=353.12 (C ₂₄ H ₁₁ D ₄ NS=353.47) Sub 2-(27) m/z=403.13 (C ₂₈ H1 ₃ D ₄ NS=403.53) Sub 2-(28) m/z=403.53 (C ₂₈ H ₁₃ D ₄ NS=403.53) Sub 2-(29) m/z=429.15 (C ₃₀ H ₁₅ D ₄ NS=429.57) Sub 2-(30) m/z=367.15 (C ₂₅ H ₁₃ D ₄ NO ₂ =367.43) Sub 2-(31) m/z=354.11 (C ₂₃ H ₁₀ D ₄ N ₂ S=354.46) Sub 2-(32) m/z=425.12 (C ₃₀ H ₁₉ NS=425.54) Sub 2-(33) m/z=389.18 (C ₂₈ H ₂₃ NO=389.49) Sub 2-(34) m/z=708.26 (C ₅₁ H ₃₆ N ₂ S=708.91) Sub 2-(35) m/z=832.29 (C ₆₁ H ₄₀ N ₂ S=833.05) Sub 2-(36) m/z=830.28 (C ₆₁ H ₃₈ N ₂ S=831.03)

3. Sub 3 Synthesis Example <Scheme 5>

(1) Sub3-1 synthesis method

The synthesized intermediate A, 9-bromo-7H-benzocarbazole, Ph(PPh ₃ ), and NaCO 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 Sub3-1.

(2) Sub 3 synthesis method

Sub 3-1 was dissolved in trifluoromethanesulfonic acid solvent, and then stirred at room temperature for 48 hours. When the reaction was completed, the reaction product was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed. 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.

<Reaction Scheme 6>

(3) Sub 3-2 synthesis

Dissolve the obtained Sub 1-2 (1 equivalent), 1-bromo-2-nitronaphthalene (1 equivalent), Pd(PPh ₃ ) ₄ (0.03 equivalent), and K ₂ CO ₃ (3 equivalent) in anhydrous THF and a small amount of water. After that, it was 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 3-1.

(4) Sub 3'Synthesis Example

The obtained Sub 3-2 (1 equivalent) and triphenylphosphine (2.5 equivalents) 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'.

Examples of Sub 3 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 3-(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 3-(2) m/z=327.10 (C ₂₂ H ₉ D ₄ NS=327.43) Sub 3-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 3-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 3-(5) m/z=379.14 (C ₂₆ H ₂₁ NS=379.52) Sub 3-(6) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 3-(7) m/z=383.13 (C ₂₈ H ₁₇ NO=383.44) Sub 3-(8) m/z=475.14 (C ₃₄ H ₂₁ NS=475.60) Sub 3-(9) m/z=429.12 (C ₂₉ H ₁₉ NOS=429.53) Sub 3-(10) m/z=400.10 (C ₂₇ H ₁₆ N ₂ S=400.49)

4. Example of Sub 4 synthesis method <Scheme 7>

(1) Sub 4-1 synthesis method

Sub 2-2 and 1-bromo-2-nitronaphthalene, 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.

(2) Sub 4 synthesis method

Sub 4-1 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 4.

Examples of Sub 4 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 4-(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 4-(2) m/z=327.10 (C ₂₂ H ₉ D ₄ NS=327.43) Sub 4-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 4-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 4-(5) m/z=379.14 (C ₂₆ H ₂₁ NS=379.52) Sub 4-(6) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 4-(7) m/z=383.13 (C ₂₈ H ₁₇ NO=383.44) Sub 4-(8) m/z=475.14 (C ₃₄ H ₂₁ NS=475.60) Sub 4-(9) m/z=429.12 (C ₂₉ H ₁₉ NOS=429.53) Sub 4-(10) m/z=400.10 (C ₂₇ H ₁₆ N ₂ S=400.49)

5. Sub 5 Synthesis Example <Scheme 8>

(1) Sub 5-1 synthesis method

The synthesized intermediate A, 9-bromo-11H-benzo[a]carbazole, Ph(PPh ₃ ), and NaCO 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 5-1.

(2) Sub 5 synthesis method

Sub 5-1 was dissolved in trifluoromethanesulfonic acid solvent and stirred at room temperature for 48 hours. When the reaction was completed, the reaction product was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed. 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 5.

<Reaction Scheme 9>

(3) Sub 5-2 synthesis

Dissolve the obtained Sub 1-2 (1 equivalent), 2-bromo-1-nitronaphthalene (1 equivalent), Pd(PPh ₃ ) ₄ (0.03 equivalent), and K ₂ CO ₃ (3 equivalent) in anhydrous THF and a small amount of water. After that, it was 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 5-2.

(4) Sub 5'Synthesis Example

The obtained Sub 5-2 (1 equivalent) and triphenylphosphine (2.5 equivalents) 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'.

Examples of Sub 5 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 5-(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 5-(2) m/z=327.10 (C ₂₂ H ₉ D ₄ NS=327.43) Sub 5-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 5-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 5-(5) m/z=379.14 (C ₂₆ H ₂₁ NS=379.52) Sub 5-(6) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 5-(7) m/z=383.13 (C ₂₈ H ₁₇ NO=383.44) Sub 5-(8) m/z=475.14 (C ₃₄ H ₂₁ NS=475.60) Sub 5-(9) m/z=429.12 (C ₂₉ H ₁₉ NOS=429.53) Sub 5-(10) m/z=400.10 (C ₂₇ H ₁₆ N ₂ S=400.49)

6. Sub 6 Synthesis Example <Scheme 10>

(1) Sub 6-1 synthesis method

Sub 2-2, 2-bromo-1-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. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated to obtain the desired Sub 6-1 by column chromatography.

(2) Sub 6 synthesis method

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.

Examples of Sub 6 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 6-(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 6-(2) m/z=327.10 (C ₂₂ H ₉ D ₄ NS=327.43) Sub 6-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 6-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 6-(5) m/z=379.14 (C ₂₆ H ₂₁ NS=379.52) Sub 6-(6) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 6-(7) m/z=383.13 (C ₂₈ H ₁₇ NO=383.44) Sub 6-(8) m/z=475.14 (C ₃₄ H ₂₁ NS=475.60) Sub 6-(9) m/z=429.12 (C ₂₉ H ₁₉ NOS=429.53) Sub 6-(10) m/z=400.10 (C ₂₇ H ₁₆ N ₂ S=400.49)

7. Sub 7 Synthesis Example <Scheme 11>

(1) Sub 7-1 synthesis method

The synthesized intermediate A, 11-bromo-9H-dibenzo[a,c]carbazole, Ph(PPh ₃ ), and NaCO 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 7-1.

(2) Sub 7 synthesis method

Sub 7-1 was dissolved in trifluoromethanesulfonic acid solvent and stirred at room temperature for 48 hours. When the reaction was completed, the reaction product was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed. 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 7.

<Reaction Scheme 12>

(3) Sub 7-2 synthesis

Dissolve the obtained Sub 1-2 (1 equivalent), 9-bromo-10-nitrophenanthrene (1 equivalent), Pd(PPh ₃ ) ₄ (0.03 equivalent), and K ₂ CO ₃ (3 equivalent) in anhydrous THF and a small amount of water. After that, it was 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.

(4) Sub 7'Synthesis Example

The obtained Sub 7-2 (1 equivalent) and triphenylphosphine (2.5 equivalents) 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'.

Examples of Sub 7 are as follows, but are not limited thereto.

*

compound FD-MS compound FD-MS Sub 7-(1) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 7-(2) m/z=377.12 (C ₂₆ H ₁₁ D ₄ NS=377.49) Sub 7-(3) m/z=449.12 (C ₃₂ H ₁₉ NS=449.56) Sub 7-(4) m/z=499.14 (C ₃₆ H ₂₁ NS=499.62) Sub 7-(5) m/z=429.16 (C ₃₀ H ₂₃ NS=429.58) Sub 7-(6) m/z=483.16 (C ₃₆ H ₂₁ NO=483.56) Sub 7-(7) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 7-(8) m/z=525.16 (C ₃₈ H ₂₃ NS=525.66) Sub 7-(9) m/z=479.13 (C ₃₃ H ₂₁ NOS=479.59) Sub 7-(10) m/z=450.12 (C ₃₁ H ₁₈ N ₂ S=450.55)

8. Example of Sub 8 synthesis method <Scheme 13>

(1) Sub 8-1 synthesis method

Sub 2-2, 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. 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 8-1 by column chromatography.

(2) Sub 8 synthesis method

Sub 8-1 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 8.

Examples of Sub 8 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 8-(1) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 8-(2) m/z=377.12 (C ₂₆ H ₁₁ D ₄ NS=377.49) Sub 8-(3) m/z=449.12 (C ₃₂ H ₁₉ NS=449.56) Sub 8-(4) m/z=499.14 (C ₃₆ H ₂₁ NS=499.62) Sub 8-(5) m/z=429.16 (C ₃₀ H ₂₃ NS=429.58) Sub 8-(6) m/z=483.16 (C ₃₆ H ₂₁ NO=483.56) Sub 8-(7) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 8-(8) m/z=525.16 (C ₃₈ H ₂₃ NS=525.66) Sub 8-(9) m/z=479.13 (C ₃₃ H ₂₁ NOS=479.59) Sub 8-(10) m/z=450.12 (C ₃₁ H ₁₈ N ₂ S=450.55)

9. Sub 9 synthesis method example <Scheme 14>

(1) Sub 9-1 synthesis method

2-bromocarbazole substituted with R ₁ to R ₄ , 1-iodo-2-(methylsulfinyl)naphthalene, Ph(PPh ₃ ), and NaCO 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 9-1.

(2) Sub 9 synthesis method

Sub 9-1 was dissolved in trifluoromethanesulfonic acid solvent and stirred at room temperature for 48 hours. When the reaction was completed, the reaction product was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed. 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 9.

<Reaction Scheme 15>

(3) Sub 9-2 synthesis

After dissolving 9-bromonaphtho[2,1-b]benzofuran (1 equivalent) substituted with R _{5 to 6} in DMF, bispinacolatodiboron (1.1 equivalent), Pd (dppf)Cl ₂ catalyst (0.03 equivalent), After adding KOAc (3 equivalents) in order and stirring for 24 hours to synthesize a borate compound, the obtained compound was separated through a silicagel column and recrystallization to obtain Sub 9-2.

(4) Sub 9-3 synthesis

The obtained Sub 9-2 (1 equivalent) and 1-bromo-2-nitrobenzene (1 equivalent) substituted with R _{1 to 4} , Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalent) are anhydrous. After dissolving in THF and a small amount of water, it was 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 9-3.

(5) Sub 9'Synthesis Example

The obtained Sub 9-3 (1 equivalent) and triphenylphosphine (2.5 equivalents) 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'.

Examples of Sub 9 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 9-(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 9-(2) m/z=327.10 (C ₂₂ H ₉ D ₄ NS=327.43) Sub 9-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 9-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 9-(5) m/z=379.14 (C ₂₆ H ₂₁ NS=379.52) Sub 9-(6) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 9-(7) m/z=383.13 (C ₂₈ H ₁₇ NO=383.44) Sub 9-(8) m/z=475.14 (C ₃₄ H ₂₁ NS=475.60) Sub 9-(9) m/z=429.12 (C ₂₉ H ₁₉ NOS=429.53) Sub 9-(10) m/z=400.10 (C ₂₇ H ₁₆ N ₂ S=400.49)

10. Sub 10 Synthesis Example <Scheme 16>

(1) Sub 10-2 synthesis method

Sub 10-1 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 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 the organic solvent was concentrated to obtain the desired Sub 10-2 by column chromatography.

(2) Sub 10-3 synthesis method

Sub 10-2 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 in an organic solvent to obtain a desired Sub 10-3 by column chromatography.

(3) Sub 10 synthesis method

Sub 10-3 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 10.

Examples of Sub 10 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 10-(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 10-(2) m/z=327.10 (C ₂₂ H ₉ D ₄ NS=327.43) Sub 10-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 10-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 10-(5) m/z=379.14 (C ₂₆ H ₂₁ NS=379.52) Sub 10-(6) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 10-(7) m/z=383.13 (C ₂₈ H ₁₇ NO=383.44) Sub 10-(8) m/z=475.14 (C ₃₄ H ₂₁ NS=475.60) Sub 10-(9) m/z=429.12 (C ₂₉ H ₁₉ NOS=429.53) Sub 10-(10) m/z=400.10 (C ₂₇ H ₁₆ N ₂ S=400.49)

11.Example of Sub 11 synthesis method <Scheme 17>

(1) Sub 11-1 synthesis method

2-bromocarbazole substituted with R ₁ to R ₄ , 2-iodo-1-(methylsulfinyl)naphthalene, Ph(PPh ₃ ), and NaCO 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 11-1.

(2) Sub 11 synthesis method

Sub 11-1 was dissolved in trifluoromethanesulfonic acid solvent, and stirred at room temperature for 48 hours. When the reaction was completed, the reaction product was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed. 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 11.

<Reaction Scheme 18>

(3) Sub 11-2 synthesis

After dissolving 9-bromonaphtho[1,2-b]benzofuran (1 equivalent) substituted with R _{5 to 6} in DMF, bispinacolatodiboron (1.1 equivalent), Pd (dppf)Cl ₂ catalyst (0.03 equivalent), After adding KOAc (3 equivalents) in order and stirring for 24 hours to synthesize a borate compound, the obtained compound was separated through a silicagel column and recrystallization to obtain Sub 11-2.

(4) Sub 11-3 synthesis

The obtained Sub 11-2 (1 equivalent) and 1-bromo-2-nitrobenzene (1 equivalent) substituted with R _{1 to 4} , Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalent) are anhydrous. After dissolving in THF and a small amount of water, it was 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 11-3.

(5) Sub 11' Synthesis Example

The obtained Sub 11-3 (1 equivalent) and triphenylphosphine (2.5 equivalents) 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'.

Examples of Sub 11 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 11-(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 11-(2) m/z=327.10 (C ₂₂ H ₉ D ₄ NS=327.43) Sub 11-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 11-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 11-(5) m/z=379.14 (C ₂₆ H ₂₁ NS=379.52) Sub 11-(6) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 11-(7) m/z=383.13 (C ₂₈ H ₁₇ NO=383.44) Sub 11-(8) m/z=475.14 (C ₃₄ H ₂₁ NS=475.60) Sub 11-(9) m/z=429.12 (C ₂₉ H ₁₉ NOS=429.53) Sub 11-(10) m/z=400.10 (C ₂₇ H ₁₆ N ₂ S=400.49)

12. Sub 12 Synthesis Example <Scheme 19>

(1) Sub 12-2 synthesis method

Sub 12-1 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 organic solvent was concentrated to obtain the desired Sub 12-2 by column chromatography.

(2) Sub 12-3 synthesis method

Sub 12-2 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 organic solvent was concentrated to obtain the desired Sub 12-3 by column chromatography.

(3) Sub 12 synthesis method

Sub 12-3 (1 equivalent) and triphenylphosphine (2.5 equivalent) 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.

Examples of Sub 12 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 12-(1) m/z=323.08 (C ₂₂ H ₁₃ NS=323.41) Sub 12-(2) m/z=327.10 (C ₂₂ H ₉ D ₄ NS=327.43) Sub 12-(3) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 12-(4) m/z=399.11 (C ₂₈ H ₁₇ NS=399.51) Sub 12-(5) m/z=379.14 (C ₂₆ H ₂₁ NS=379.52) Sub 12-(6) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 12-(7) m/z=383.13 (C ₂₈ H ₁₇ NO=383.44) Sub 12-(8) m/z=475.14 (C ₃₄ H ₂₁ NS=475.60) Sub 12-(9) m/z=429.12 (C ₂₉ H ₁₉ NOS=429.53) Sub 12-(10) m/z=400.10 (C ₂₇ H ₁₆ N ₂ S=400.49)

13. Sub 13 Synthesis Example <Scheme 20>

(1) Sub 13-1 synthesis method

2-bromocarbazole substituted with R ₁ to R ₄ , 9-iodo-10-(methylsulfinyl)phenanthrene, Ph(PPh ₃ ), and NaCO 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 13-1.

(2) Sub 13 synthesis method

Sub 13-1 was dissolved in trifluoromethanesulfonic acid solvent and stirred at room temperature for 48 hours. When the reaction was completed, the reaction product was poured into a mixed solvent of water and pyridine, and refluxed for 20 minutes. The reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and washed. 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.

<Reaction Scheme 21>

(3) Sub 13-2 synthesis

After dissolving 11-bromophenanthro[9,10-b]benzofuran (1 equivalent) substituted with R _{5 to 6} in DMF, bispinacolatodiboron (1.1 equivalent), Pd (dppf)Cl ₂ catalyst (0.03 equivalent), After adding KOAc (3 equivalents) in order and stirring for 24 hours to synthesize a borate compound, the obtained compound was separated through a silicagel column and recrystallization to obtain Sub 13-2.

(4) Sub 13-3 synthesis

The obtained Sub 13-2 (1 equivalent) and 1-bromo-2-nitrobenzene (1 equivalent) substituted with R _{1 to 4} , Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalent) are anhydrous. After dissolving in THF and a small amount of water, it was 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 13-3.

(5) Sub 13' Synthesis Example

The obtained Sub 13-3 (1 equivalent) and triphenylphosphine (2.5 equivalents) 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'.

Examples of Sub 13 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 13-(1) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 13-(2) m/z=377.12 (C ₂₆ H ₁₁ D ₄ NS=377.49) Sub 13-(3) m/z=449.12 (C ₃₂ H ₁₉ NS=449.56) Sub 13-(4) m/z=499.14 (C ₃₆ H ₂₁ NS=499.62) Sub 13-(5) m/z=429.16 (C ₃₀ H ₂₃ NS=429.58) Sub 13-(6) m/z=483.16 (C ₃₆ H ₂₁ NO=483.56) Sub 13-(7) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 13-(8) m/z=525.16 (C ₃₃ H ₂₁ NOS=525.66) Sub 13-(9) m/z=479.13 (C ₃₃ H ₂₁ NOS=479.59) Sub 13-(10) m/z=450.12 (C ₃₁ H ₁₈ N ₂ S=450.55)

14. Sub 14 Synthesis Example <Scheme 22>

(1) Sub 14-2 synthesis method

Sub 14-1 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 organic solvent was concentrated to obtain the desired Sub 14-2 by column chromatography.

(2) Sub 14-3 synthesis method

Sub 14-2 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 organic solvent was concentrated to obtain the desired Sub 14-3 by column chromatography.

(3) Sub 14 synthesis method

Sub 14-3 (1 equivalent) and triphenylphosphine (2.5 equivalent) 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.

Examples of Sub 14 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 14-(1) m/z=373.09 (C ₂₆ H ₁₅ NS=373.47) Sub 14-(2) m/z=377.12 (C ₂₆ H ₁₁ D ₄ NS=377.49) Sub 14-(3) m/z=449.12 (C ₃₂ H ₁₉ NS=449.56) Sub 14-(4) m/z=499.14 (C ₃₆ H ₂₁ NS=499.62) Sub 14-(5) m/z=429.16 (C ₃₀ H ₂₃ NS=429.58) Sub 14-(6) m/z=483.16 (C ₃₆ H ₂₁ NO=483.56) Sub 14-(7) m/z=433.15 (C ₃₂ H ₁₉ NO=433.50) Sub 14-(8) m/z=525.16 (C ₃₃ H ₂₁ NOS=525.66) Sub 14-(9) m/z=479.13 (C ₃₃ H ₂₁ NOS=479.59) Sub 14-(10) m/z=450.12 (C ₃₁ H ₁₈ N ₂ S=450.55)

Examples of Sub 15 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 15-3 m/z=308.02 (C ₁₈ H ₁₃ Br=309.20) Sub 15-4 m/z=321.02 (C ₁₈ H ₁₂ BrN=322.20) Sub 15-5 m/z=311.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 15-6 m/z=311.01 (C ₁₅ H ₁₀ BrN ₃ =312.16) Sub 15-7 m/z=283.99 (C ₁₄ H ₉ BrN ₂ =285.14) Sub 15-8 m/z=387.04 (C ₂₁ H ₁₄ BrN ₃ =388.26) Sub 15-9 m/z=463.07 (C ₂₇ H ₁₈ BrN ₃ =464.36) Sub 15-10 m/z=503.10 (C ₃₀ H ₂₂ BrN ₃ =504.42) Sub 15-11 m/z=385.05 (C ₂₃ H ₁₆ BrN=386.28) Sub 15-12 m/z=386.04 (C ₂₂ H ₁₅ BrN ₂ =387.27) Sub 15-13 m/z=385.05 (C ₂₃ H ₁₆ BrN=386.28) Sub 15-14 m/z=360.03 (C ₂₀ H ₁₃ BrN ₂ =361.23) Sub 15-15 m/z=386.04 (C ₂₂ H ₁₅ BrN ₂ =387.27) Sub 15-16 m/z=310.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 15-17 m/z=386.04 (C ₂₂ H ₁₅ BrN ₂ =387.27) Sub 15-18 m/z=387.04 (C ₂₁ H ₁₄ BrN ₃ =388.26) Sub 15-19 m/z=310.01 (C ₁₆ H ₁₁ BrN ₂ =311.18) Sub 15-20 m/z=283.99 (C ₁₄ H ₉ BrN ₂ =285.14) Sub 15-21 m/z=374.01 (C ₂₀ H ₁₁ BrN ₂ O=375.2) Sub 15-22 m/z=400.06 (C ₂₃ H ₁₇ BrN ₂ =401.30) Sub 15-23 m/z=360.03 (C ₂₀ H ₁₃ BrN ₂ =361.23) Sub 15-24 m/z=476.09 (C ₂₉ H ₂₁ BrN ₂ =477.39) Sub 15-25 m/z=284.99 (C ₁₃ H ₈ BrN ₃ =286.13) Sub 15-26 m/z=284.99 (C ₁₃ H ₈ BrN ₃ =286.13) Sub 15-27 m/z=284.99 (C ₁₃ H ₈ BrN ₃ =286.13) Sub 15-28 m/z=375.00 (C ₁₉ H ₁₀ BrN ₃ O=376.2) Sub 15-29 m/z=401.05 (C ₂₂ H ₁₆ BrN ₃ =402.29)

Product synthesis example: Sub 1, Sub 2, Sub 3, Sub 4, Sub 5, Sub 6, Sub 7, Sub 8, Sub 9, Sub 10, Sub 11, Sub 12, Sub 13 or Sub 14 (1 equivalent ) And Sub 15 (1.1 eq) in toluene, Pd ₂ (dba) ₃ (0.05 eq), PPh ₃ (0.1 eq), NaO t -Bu (3 eq) 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 Products.

(1) Product 16 synthesis example

Five-membered hetero compounds (7.0g, 20mmol) and 2-brom-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 , concentrated, and the resulting organic material was recrystallized with a silicagel column to give 7.5 g (yield 65%).

(2) Product 32 synthesis example

After mixing the five-membered hetero compound (9.3g, 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 7.4 g (yield 68%).

(3) Product 60 synthesis example

Five-atom hetero compounds (6.5g, 20mmol) and 4-(4-bromophenyl)-2,6-diphenylpyrimidine (9.3g, 24mmol) were mixed in toluene, followed by Pd ₂ (dba) ₃ , PPh ₃ , NaOt-Bu, 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 7.8 g (62% yield).

(4) Synthesis example of Product 75

Pd ₂ (dba) ₃ after mixing a five-membered hetero compound (6.5g, 20mmol) and 2-(4-bromophenyl)-1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol) in toluene, After each addition of PPh ₃ and NaOt-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 give 7.5 g (yield 63%).

(5) Product 82 synthesis example

Five-membered hetero compounds (7.5g, 20mmol) and 2-brom-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 give 7.9 g (yield 65%).

(6) Synthesis example of Product 103

Pd ₂ (dba) ₃ after mixing a five-membered hetero compound (7.5g, 20mmol) and 2-(4-bromophenyl)-1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol) in toluene, After each addition of PPh ₃ and NaOt-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 8.1 g (yield 63%).

(7) Product 105 synthesis example

Five-membered hetero compounds (5.6g, 20mmol) and bromobenzene (3.8g, 24mmol) were mixed in toluene, and then Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added respectively, followed by stirring and refluxing 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 5.0 g (70% yield).

(8) Product 200 synthesis example

After mixing a five-membered hetero compound (8.1g, 20mmol) and 2-(4-bromophenyl)-benzoimidazole (6.6 g, 24mmol) in toluene, 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 7.4 g (62% yield).

(9) Product 211 synthesis example

Five-atom hetero compounds (9.0g, 20mmol) and 2-(4-bromophenyl)-4,6-diphenylpyrimidine (9.3g, 24mmol) were mixed in toluene, followed by Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu, 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 9.8 g (yield 65%).

(10) Product 225 synthesis example

Five-atom hetero compounds (9.0g, 20mmol) and 2-(4-bromophenyl)-4,6-diphenylpyrimidine (9.3g, 24mmol) were mixed in toluene, followed by Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu, 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 give 10.0 g (yield 66%).

(11) Product 231 synthesis example

Five-atom hetero compound (7.5g, 20mmol) and 2-bromonaphthalene (5.0g, 24mmol) were mixed in toluene, then Pd ₂ (dba) ₃ , PPh ₃ , NaOt-Bu were added, respectively, and stirred 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 give 6.8 g (yield 68%).

(12) Synthesis example of Product 255

After mixing a five-membered hetero compound (9.0g, 20mmol) and 2-(4-bromophenyl)-1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4g, 24mmol) in toluene, Pd ₂ (dba) ₃ , After each addition of PPh ₃ and NaOt-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 give 9.4 g (yield 65%).

(13) Product 257 synthesis example

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 give 4.5 g (yield 63%).

(14) Synthesis example of Product 272

Five-membered hetero compounds (7.0g, 20mmol) and 2-brom-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 , concentrated, and the resulting organic material was recrystallized with a silicagel column to give 7.5 g (yield 65%).

(15) Product 288 synthesis example

After mixing the five-membered hetero compound (9.3g, 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 with MgSO ₄ and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 7.4 g (yield 68%).

(16) Product 315 synthesis example

Five-atom hetero compounds (9.7g, 20mmol) and 2-(4-bromophenyl)-4,6-diphenylpyrimidine (9.3g, 24mmol) were mixed in toluene, followed by Pd ₂ (dba) ₃ , PPh ₃ , NaOt-Bu, 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 , concentrated, and the resulting organic material was recrystallized with a silicagel column to give 12.7 g (yield 67%).

(17) Product 324 synthesis example

Five-membered hetero compounds (9.7g, 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 give 11.5 g (yield 69%).

(18) Product 339 synthesis example

After mixing the five-membered hetero compound (7.1g, 20mmol) and 2-bromo-4,6-diphenylpyrimidine (7.5g, 24mmol) in toluene, 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 7.2 g (yield 61%).

(19) Product 359 synthesis example

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 8.0 g (62% yield).

Manufacturing evaluation of organic electric devices

[Experimental Example 1] (Applied to a light emitting 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, on the ITO layer (anode) formed on a glass substrate, N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ^1- A phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a hole injection layer with a thickness of 60 nm. Subsequently, 4,4-bis[ N- (1-naphthyl) -N -phenylamino]biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 20 nm on the hole injection layer to form a hole transport layer. . Next, a light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by doping with a weight of 95:5 using the compound of the present invention as a host material and Ir(ppy) ₃ [tris(2-phenylpyridine)-iridium] as a dopant material. I did. 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 to form a hole blocking layer. , Tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Comparative Example 1]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, but a light emitting layer was formed using Comparative Compound 1 as a light emitting host instead of the compound of the present invention.

<Comparative compound 1>

[Comparative Example 2]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, but a light emitting layer was formed using Comparative Compound 2 as a light emitting host instead of the compound of the present invention.

<Comparative compound 2>

[Comparative Example 3]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, but a light emitting layer was formed using Comparative Compound 3 instead of the compound of the present invention as a light emitting host.

<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 T95 life was measured through a life measurement equipment manufactured by McScience. Table 17 below shows device fabrication and evaluation results for Examples and Comparative Examples to which the compounds according to the present invention are applied, and organic electric devices manufactured according to Experimental Example 1 are shown as Examples 1 to 360.

As confirmed in the above table, the compounds of the present invention exhibit higher luminous efficiency and higher lifetime than Comparative Examples 1 to 3, and in particular, lower driving voltage, higher efficiency, and higher lifetime than Comparative Examples 2 and 3 Represents. It is judged that the HOMO of the core becomes deeper by introducing a substituent into the five-atomic heterocyclic backbone, and has an appropriate HOMO value with HTL, which increases the lifespan by increasing hole mobility. Also, the electron of LUMO due to the substituent of the backbone It is judged that the density is delocalized, indicating high efficiency.

The organic electroluminescent device using the material for an organic electroluminescent device of the present invention can be used as a light emitting host material to remarkably improve color purity, high luminous efficiency and lifetime, and the compounds of the present invention can be used in other organic material layers of the organic electroluminescent device, For example, even if it is used for a hole injection layer, a light emission auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.

The above description is merely illustrative of the present invention, and those 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 describe 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 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 (6)

Compound represented by the following formula (2):
<Formula 2>

In Chemical Formula 2,
Y is S or O,
L is a single bond; C ₆ ~ C ₁₈ arylene group; Fluorenylene group; And O, N, S, Si and P is selected from the group consisting of a C ₂ ~ C ₁₂ heterocyclic group containing at least one heteroatom, except for a single bond C ₆ ~ C ₂₀ aryl group or C ₂ ~ C ₂₀ may be substituted with a heterocyclic group,
Ar ₁ is a C ₆ ~ C ₁₈ aryl group; Fluorenyl group; And O, N, S, Si and P is selected from the group consisting of a C ₃ ~ C ₁₂ heterocyclic group containing at least one heteroatom,
R ₁ to R ₄ and R ₇ to R ₁₀ are each independently hydrogen; heavy hydrogen; C ₆ ~ C ₁₈ aryl group; Fluorenyl group; O, N, S, Si, and C ₃ ~ C ₁₂ heterocyclic group containing at least one heteroatom of P; C ₁ ~ C ₁₀ alkyl group; And -LN(R')(R") is selected from the group consisting of, wherein L is a single bond, and R'and R" are each independently an aryl group or fluorenyl group of C ₆ to C ₁₈ , provided that , Ⅰ) One of R ₁ to R ₄ is -LN(R')(R"), and all of R ₇ to R ₁₀ are hydrogen, or ii) one of R ₇ to R ₁₀ is -LN(R')( R"), and R ₁ to R ₄ are all hydrogen,
R ₅ and R ₆ are hydrogen,
When the R ₁ to R ₄ , R ₇ to R ₁₀ , Ar ₁ , R', R" are aryl groups, each of them is deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ - an alkyl group of C _20, C ₂ - C ₂₀ alkene group, C ₆ ~ C ₂₀ aryl group, of a C ₆ - C ₂₀ substituted by deuterium aryl group, a C ₂ ~ C ₂₀ of the heterocyclic group and C ₃ ~ It may be substituted with one or more substituents selected from the group consisting of C ₂₀ cycloalkyl groups,
When the R ₁ to R ₄ , R ₇ to R ₁₀ , and Ar ₁ are heterocyclic groups, each of them is deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group , C cycloalkyl group of ₂ ~ C ₂₀ alkenyl group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted with heavy hydrogen in the It may be substituted with one or more substituents selected from the group consisting of,
When the R ₁ to R ₄ , R ₇ to R ₁₀ , Ar ₁ , R', R" are fluorenyl groups, each of them is deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkyl group, C ₂ ~ C ₂₀ of the alkenyl group, consisting of a cycloalkyl group of C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted by deuterium May be substituted with one or more substituents selected from the group,
When the R ₁ to R ₄ and R ₇ to R ₁₀ are alkyl groups, each of them is a halogen, a silane group, a cyano group, a C ₁ to C ₂₀ alkoxyl group, a C ₁ to C ₂₀ alkyl group, and a C ₂ to C ₂₀ of which may be substituted with an alkenyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ aryl group substituted with a heavy hydrogen and one or more substituents selected from the group consisting of a heterocyclic C ₂ ~ C _20. The method of claim 1,
The compound represented by Formula 2 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, wherein the organic material layer contains the compound of claim 1. The method of claim 3,
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 3; And
A control unit driving the display device; Electronic device comprising a. The method of claim 5,
The organic electroluminescent device is an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and an electronic device, characterized in that one of a single color or white lighting device.

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