KR20180132017A - 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 containing a heteroaromatic heterocycle capable of improving the luminous efficiency, stability and lifetime of the device, and an organic electronic device using the same and an electronic device thereof.

Description

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

TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

On the other hand, the diffusion of metal oxide from the anode electrode (ITO), which is one of the causes of shortening the lifetime of the organic electronic device, is delayed, and stable characteristics such as joule heating generated during driving the device, It is necessary to develop a hole injection layer material having a temperature. It is also reported that the low glass transition temperature of the hole transporting layer material significantly affects the lifetime of the device depending on the characteristics of the uniformity of the thin film surface collapsing during device operation. In addition, the deposition method is the mainstream in the formation of OLED devices, and a material that can withstand such a long time, that is, a material having high heat resistance characteristics, is required.

In order to sufficiently exhibit the excellent characteristics of the organic electroluminescent device described above, a material constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material is supported by a stable and efficient material However, stable and efficient development of an organic material layer for an organic electric device has not yet been sufficiently developed, and therefore development of a new material is continuously required.

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

In one aspect, the invention provides compounds represented by the formula:

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

By using the compound according to the present invention, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the device, and can greatly improve the color purity and lifetime of the device.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.
Figure 2 shows the formula according to one aspect of the invention.

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

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference symbols as possible even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

The term " halo " or " halogen " as used herein, on the other hand, includes fluorine, chlorine, bromine, and iodine unless otherwise specified.

The term " alkyl " or " alkyl group ", as used herein, unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.

The term " alkenyl " or " alkynyl ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms,

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

The term " alkoxy group " as used in the present invention has, unless otherwise stated, 1 to 60 carbon atoms, but is not limited thereto.

The terms " aryl group " and " arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto.

In the present invention, an aryl group or an arylene group means an aromatic group having a single ring or a heterocyclic ring, and the neighboring substituent includes an aromatic ring formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

The term " heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term " heteroaryl group " or " heteroarylene group " as used in the present invention means an aryl or arylene group having 3 to 60 carbon atoms each containing at least one heteroatom, But includes a single ring as well as a heterocyclic ring and may be formed by bonding adjacent groups.

The term " heterocycloalkyl ", " heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, , And neighboring groups may be combined with each other. Furthermore, the "heterocyclic group" may mean an alicyclic group and / or an aromatic group including a hetero atom.

As used herein, the term " heteroatom " refers to N, O, S, P and Si, unless otherwise indicated.

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

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

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention alkoxy group, C ₁ ~ C ₂₀ alkyl amine group of _20, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron of Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a cyano group, a germanium group, and a C ₅ to C ₂₀ heterocyclic group, and is not limited to these substituents.

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

1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110, ) Having an organic compound layer containing a compound represented by the general formula (1). In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

Also, although not shown, the organic electroluminescent 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 may be used as a host or a dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, .

The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.

In addition, the organic material layer can be formed using a variety of polymer materials by a solution process other than a vapor deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, It can be made of 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 electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

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

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

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

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

≪ Formula 1 >

In the above formulas,

R ₁ to R ₄ and R ₇ to R ₁₀ are independently selected from the group consisting of hydrogen, deuterium, halogen, C ₆ to C ₆₀ aryl, fluorenyl, C ₃ to C ₆₀ aliphatic rings and C ₆ to C fused ring group of the ring _60, O, N, S, Si, and a heterocyclic group of C ₂ ~ C ₆₀ containing at least one hetero atom of P, -LN (R ') ( R "), C 1 ~ C ₅₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ alkoxy group of C ₃₀ and C ₆ ~ C ₃₀ aryloxy group or selected from the group consisting of the, or ⅱ) adjacent groups combine with each other at least between (Wherein the group which 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 hydrogen at the same time is excluded.

In addition, in (ii), adjacent groups of R ₁ to R ₄ and R ₇ to R _{10 may} combine with each other to form at least one ring. R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₇ and R ₈ , R ₈ and R ₉ and / or R ₉ and R ₁₀ are bonded to each other to form a ring. At this time, since it is important that neighboring groups bond together to form a ring, the scope of the present invention is not limited by what kind of substituent and which reaction forms the ring. In this case, the ring may be substituted with other known reactions (Heck 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.).

The ring formed by bonding adjacent groups of R ₁ to R ₄ and R ₇ to R ₁₀ to each other may be a monocyclic or polycyclic aromatic ring or a heterocyclic ring containing at least one heteroatom as well as an aromatic ring and an aliphatic ring are fused It may also be in the form of Illustratively, neighboring groups of R ₁ and R _{10 may} be bonded to each other to form an aromatic ring such as benzene, naphthalene, phenanthrene, etc., and the number of carbon atoms in the aromatic ring formed 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 bond to each other to form a benzene ring, a phenanthrene form may be formed together with a benzene ring of the coupled parent.

In addition, neighboring groups of 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., have. In the case of a polycyclic ring, they may be fused to each other, the plural rings may not be fused with each other, or the fused and non-fused forms may be mixed.

R ₅ and R ₆ are independently of each other hydrogen, deuterium, halogen, a C ₆ to C ₆₀ aryl group, a fluorenyl group, a C ₃ to C ₆₀ aliphatic ring and a C ₆ to C ₆₀ aromatic ring A C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P, -LN (R ') (R "), a C ₁ to C ₅₀ alkyl group, A C ₂ to C ₂₀ alkenylene group, a C ₁ to C ₃₀ alkoxy group, and a C ₆ to C ₃₀ aryloxy group.

In the above formulas, X and Y are independently of each other S, O or -Si (R ₁₁ ) (R ₁₂ ). Wherein R ₁₁ and R ₁₂ are independently selected from the group consisting of hydrogen, a C ₆ to C ₆₀ aryl group, a fluorenyl group, a C ₂ to C ₆₀ group containing at least one heteroatom selected from O, N, S, Si and P A heterocyclic group, or a C ₁ to C 50 alkyl group. On the other hand, each of m and n may be 0 or 1, except that m and n are both 0s. That is, since m + n = 1 or more, at least one of X and Y must be present.

L is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; And a divalent aliphatic hydrocarbon group. The group excluding a single bond may be a nitro group, a cyano group, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, a C ₂ to C ₂₀ heterocyclic group, a C ₁ to C ₂₀ alkoxy Group and an amino group.

Ar ₁ is a C ₂ to C ₆₀ heterocyclic group, a C ₆ to C ₆₀ aryl group, a fluorenyl group or -N (R (O) ') (R "),

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

On the other hand, the R ₁ ~ R _10, Ar _1, R ', R ", R ₁₁ and R, if ₁₂ is an aryl group, which is heavy hydrogen, a halogen, a silane group, a boron group, a germanium group, a cyano group, a 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 An aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₂ to C ₂₀ heterocyclic group, a C ₃ to C ₂₀ cycloalkyl group, a C ₇ to C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,

Wherein _{R 1 ~ R 10, Ar 1} , R ', R ", R 11 and R ₁₂ are, if the heterocyclic group, which is heavy hydrogen, an alkoxyl group, a halogen, a silane group, a cyano group, a nitro group, C ₁ ~ C _20, 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 A cycloalkyl group having ₃ to ₂₀ carbon atoms, a cycloalkyl group having ₇ to ₂₀ carbon atoms An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,

Wherein _{R 1 ~ R 10, Ar 1} , R ', R ", R 11 and R ₁₂ is fluorenyl if weather in which heavy hydrogen, a halogen, a silane group, a cyano group, C alkyl group of ₁ ~ C _20, C ₂ ~ 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 Which may be substituted with one or more substituents selected,

When R ₁ to R ₁₀ are fused ring groups, they may be substituted with one or more substituents selected from the group consisting of deuterium, halogen, silane, boron, germanium, cyano, nitro, C ₁ to C ₂₀ alkylthio, C ₁ to C ₂₀ alkoxyl , 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, A C ₂ to C ₂₀ heterocyclic group, a C ₃ to C ₂₀ cycloalkyl group, a C ₇ to C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,

When R ₁ to R ₁₂ are an alkyl group, it is preferably 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, An aryl group having ₆ to ₂₀ carbon atoms, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₂ to C ₂₀ heterocyclic group, a C ₇ to C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,

When R ₁ to R ₁₀ are alkenyl groups, they may be substituted by deuterium, a halogen, a silane 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, a 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 An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,

When R ₁ to R ₁₀ are alkoxyl groups, they may be substituted by 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 group substituted with deuterium, A C ₂ to C ₂₀ heterocyclic group, and a C ₃ to C ₂₀ cycloalkyl group, each of which may be substituted with at least one substituent selected from the group consisting of

When R ₁ to R ₁₀ are aryloxy groups, they may be substituted by 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 , A C ₂ to C ₂₀ heterocyclic group, and a C ₃ to C ₂₀ cycloalkyl group.

In the formula (1), when n = 0, m = 0, the following formula (3) can be obtained.

            &Lt; Formula 2 > < EMI ID =

,

,

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

When all of R ₁ to R ₄ are hydrogen, R ₁ and R ₂ are bonded to each other to form a benzene ring, and when R ₃ and R ₄ are hydrogen, , 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 ₁ and R ₂ bond to each other to form a benzene ring, and R ₃ And R ₄ are bonded to each other to form a benzene ring,

When all of R ₇ to R ₁₀ are hydrogen, R ₇ and R ₈ are bonded to each other to form a benzene ring, and when R ₉ and R ₁₀ are hydrogen, and the like, R ₁ and R ₂ is hydrogen and R ₃ and R ₄ are bonded to each other to be formed to a benzene ring as shown in formula 10, R ₇ and R ₈ and at the same time _to form a benzene ring bonded to each other R ₉ and R ₁₀ may be bonded to each other to form a benzene ring.

Similarly, the formula (3) may be represented by one of the following formulas.

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

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

Synthetic example

Illustratively, the compound according to the present invention can be prepared by the following Synthesis Example 1 or 2, and when adjacent groups of R ₁ to R ₄ and R ₇ to R ₁₀ are bonded to each other to form a ring, 3 or 4, or the like. In this case, the ring may be substituted with other known reactions (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.).

&Lt; Synthesis Example 1 &

&Lt; Synthesis Example 2 &

&Lt; Synthesis Example 3 &

&Lt; Synthesis Example 4 &

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

Examples of synthetic methods

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

<Reaction Scheme 1>

The starting materials (Sub 1 to Sub 14 materials and the like) may be prepared by the following reaction schemes, but may be prepared according to Synthesis Example 1 and Synthesis Example 2 as described above. Therefore, the production of the Sub material described below is merely a synthesis example, and the scope of the right of the present invention is not limited by these synthesis examples.

1-1. Sub 1 synthesis example (when X or Y is S)

<Reaction Scheme 2>

(1) Sub1-1 synthesis method

The synthesized intermediate A and 2-bromocarbazole, Ph (PPh ₃ ), and NaCO ₃ substituted with R ₁ to R ₄ were dissolved in anhydrous THF and a small amount of water, and the mixture was refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 1-1.

(2) Sub 1 synthesis method

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

1-2. Sub 1 'Synthetic method example (when X or Y is O)

<Reaction Scheme 3>

*

(1) Sub 1-2 Synthesis

After dissolving 3-bromodibenzo [b, d] furan (1 eq.) In DMF, bispinacolatodiborone (1.1 eq.), Pd (dppf) Cl ₂ catalyst (0.03 eq.) And KOAc And the mixture was stirred for 24 hours to synthesize a borate compound. Subsequently, the obtained compound was separated by silicagel column and recrystallization to obtain Sub 1-2.

(2) Sub 1-3 synthesis

Obtained Sub 1-2 (1 eq) and R _{1 ~ 4} for the 1-bromo-2-nitrobenzene ( 1 _{eq), Pd (PPh 3) 4} (0.03 eq), K ₂ CO _{3 (3} eq) in anhydrous substituted Dissolved in THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 1-3.

(3) Sub 1 'Synthetic Example

The resulting Sub 1-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 h. 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 (Reaction Scheme 4)

(1) Sub 2-2 Synthesis method

Sub 2-1 was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) was slowly added dropwise, and then the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 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. The resulting product was subjected to column chromatography to obtain the desired Sub 2-2.

(2) Sub 2-3 Synthesis method

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

(3) Sub 2 synthesis method

Sub 2-3 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After 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 include, but are not limited to, the following.

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. Example of Sub 3 Synthesis Method (Reaction Scheme 5)

(1) Sub3-1 synthesis method

The synthesized intermediate A and 9-bromo-7H-benzocarbazole, Ph (PPh ₃ ) and NaCO ₃ were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, 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 and stirred at room temperature for 48 hours. When the reaction was completed, the reaction mixture was poured into a mixed solvent of water and pyridine and refluxed for 20 minutes. The temperature of the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped off. 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

Pd (PPh ₃ ) ₄ (0.03 eq.) And K ₂ CO ₃ (3 eq.) Were dissolved in anhydrous THF and a small amount of water to obtain Sub 1-2 (1 equivalent), 1-bromo-2-nitronaphthalene After reflux, reflux was performed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , 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 'Synthetic Example

The resulting Sub 3-2 (1 eq) and triphenylphosphine (2.5 eq) 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 include, but are not limited to, the following.

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 (Reaction Scheme 7)

(1) Sub 4-1 Synthesis method

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

(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 include, but are not limited to, the following.

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. Example of Sub 5 Synthesis Method (Reaction Scheme 8)

(1) Sub 5-1 Synthesis method

The synthesized intermediate A and 9-bromo-11H-benzo [a] carbazole, Ph (PPh ₃ ) and NaCO ₃ were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , 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 a solvent of trifluoromethanesulfonic acid, and the mixture was stirred at room temperature for 48 hours. When the reaction was completed, the reaction mixture was poured into a mixed solvent of water and pyridine and refluxed for 20 minutes. The temperature of the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped off. 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.

<Reaction Scheme 9>

(3) Sub 5-2 Synthesis

Pd (PPh ₃ ) ₄ (0.03 eq.) And K ₂ CO ₃ (3 eq.) Were dissolved in anhydrous THF and a small amount of water to obtain Sub 1-2 (1 equivalent), 2-bromo-1-nitronaphthalene After reflux, reflux was performed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , 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.

(4) Sub 5 'Synthetic Example

The resulting Sub 5-2 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 h. 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 include, but are not limited to, the following.

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. Example of Sub 6 Synthesis Method <Reaction formula 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 refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. The water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was subjected to column chromatography to obtain the desired Sub 6-1.

(2) Sub 6 synthesis method

Sub 6-1 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After 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 include, but are not limited to, the following.

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. Example of Sub 7 Synthesis Method (Reaction Scheme 11)

(1) Sub 7-1 synthesis method

The synthesized intermediate A and 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 refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , 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 and stirred at room temperature for 48 hours. When the reaction was completed, the reaction mixture was poured into a mixed solvent of water and pyridine and refluxed for 20 minutes. The temperature of the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped off. 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.

<Reaction Scheme 12>

(3) Sub 7-2 synthesis

Sub-1-2 (1 equivalent), 9-bromo-10-nitrophenanthrene (1 equivalent), Pd (PPh ₃ ) ₄ (0.03 eq) and K ₂ CO ₃ (3 eq.) Were dissolved in anhydrous THF and a small amount of water After reflux, reflux was performed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 7-2.

(4) Sub 7 'Synthetic Example

The resulting Sub 7-2 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 h. 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 include, but are not limited to, the following.

*

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 <Reaction Scheme 13>

(1) Sub 8-1 synthesis method

Sub 2-2 and 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 refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. Water in the reaction mixture was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and then the organic solvent was concentrated. The resulting product was subjected to column chromatography to obtain the desired Sub 8-1.

(2) Sub 8 synthesis method

Sub 8-1 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After 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 include, but are not limited to, the following.

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. Example of Sub 9 Synthesis Method <Reaction Scheme 14>

(1) Sub 9-1 Synthesis method

2-bromocarbazole substituted with R ₁ to R ₄ and 1-iodo-2- (methylsulfinyl) naphthalene, Ph (PPh ₃ ) and NaCO ₃ were dissolved in a small amount of anhydrous THF and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, 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 and stirred at room temperature for 48 hours. When the reaction was completed, the reaction mixture was poured into a mixed solvent of water and pyridine and refluxed for 20 minutes. The temperature of the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped off. 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 eq.) Substituted with R _5-6 in DMF, bispinacolatodiaboron (1.1 eq.), Pd (dppf) Cl ₂ catalyst (0.03 eq.), KOAc (3 eq.) Were added in this order and stirred for 24 hours to synthesize a borate compound. Subsequently, the obtained compound was separated by silicagel column and recrystallization to obtain Sub 9-2.

(4) Sub 9-3 synthesis

Obtained Sub 9-2 (1 eq) and R _{1 ~ 4} for the 1-bromo-2-nitrobenzene ( 1 _{eq), Pd (PPh 3) 4} (0.03 eq), K ₂ CO _{3 (3} eq) in anhydrous substituted Dissolved in THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, 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 resulting Sub 9-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 h. After 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 include, but are not limited to, the following.

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. Example of Sub 10 synthesis (Reaction Scheme 16)

(1) Sub 10-2 Synthesis method

Sub 10-1 was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) was slowly added dropwise, and then the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 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. The resulting product was subjected to column chromatography to obtain the desired Sub 10-2.

(2) Sub 10-3 Synthesis method

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

(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 include, but are not limited to, the following.

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

After dissolved the 2-bromocarbazole and 2-iodo-1- (methylsulfinyl) naphthalene, Ph (PPh 3), NaCO 3 is substituted by R ₁ ~ R ₄ in anhydrous THF and a small amount of water and the mixture was refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, 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 and stirred at room temperature for 48 hours. When the reaction was completed, the reaction mixture was poured into a mixed solvent of water and pyridine and refluxed for 20 minutes. The temperature of the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped off. 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.

<Reaction Scheme 18>

(3) Sub 11-2 Synthesis

After dissolving 9-bromonaphtho [1,2-b] benzofuran (1 eq.) Substituted with R _5-6 in DMF, bispinacolatodiborone (1.1 eq.), Pd (dppf) Cl ₂ catalyst (0.03 eq.), KOAc (3 eq.) Were added in this order, followed by stirring for 24 hours to synthesize a borate compound. Subsequently, the obtained compound was separated by silicagel column and recrystallization to obtain Sub 11-2.

(4) Sub 11-3 Synthesis

Obtained Sub 11-2 (1 eq) and R _{1 ~ 4} for the 1-bromo-2-nitrobenzene ( 1 _{eq), Pd (PPh 3) 4} (0.03 eq), K ₂ CO _{3 (3} eq) in anhydrous substituted Dissolved in THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, 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 resulting Sub 11-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 h. After 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 include, but are not limited to, the following.

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. Example of Sub 12 synthesis method (Reaction Scheme 19)

(1) Sub 12-2 Synthesis method

Sub 12-1 was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) was slowly added dropwise, and then the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 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. The resulting product was subjected to column chromatography to obtain the desired Sub 12-2.

(2) Sub 12-3 Synthesis method

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

(3) Sub 12 synthesis method

Sub 12-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 h. After 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 include, but are not limited to, the following.

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. Example of Sub 13 Synthesis Method <Reaction formula 20>

(1) Sub 13-1 Synthesis method

2-bromocarbazole substituted with R ₁ to R ₄ and 9-iodo-10- (methylsulfinyl) phenanthrene, Ph (PPh ₃ ) and NaCO ₃ were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , 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 and stirred at room temperature for 48 hours. When the reaction was completed, the reaction mixture was poured into a mixed solvent of water and pyridine and refluxed for 20 minutes. The temperature of the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped off. 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 eq.) Substituted with R _5-6 in DMF, bispinacolatodiborone (1.1 eq.), Pd (dppf) Cl ₂ catalyst (0.03 eq.), KOAc (3 eq.) Were added in this order and stirred for 24 hours to synthesize a borate compound. Subsequently, the obtained compound was separated by silicagel column and recrystallization to obtain Sub 13-2.

(4) Sub 13-3 synthesis

Obtained Sub 13-2 (1 eq) and R _{1 ~ 4} for the 1-bromo-2-nitrobenzene ( 1 _{eq), Pd (PPh 3) 4} (0.03 eq), K ₂ CO _{3 (3} eq) in anhydrous substituted Dissolved in THF and a small amount of water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , 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 'Synthetic Example

The resulting Sub 13-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 h. 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 include, but are not limited to, the following.

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. Example of Sub 14 Synthesis Method <Reaction Formula 22>

(1) Sub 14-2 Synthesis method

Sub 14-1 was dissolved in anhydrous THF, the temperature of the reaction 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. Then, the temperature of the reaction was lowered to -78 ° C, trimethyl borate was added dropwise, and the mixture was stirred at room temperature for 12 hours. When the reaction was completed, 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. The resulting product was subjected to column chromatography to obtain the desired Sub 14-2.

(2) Sub 14-3 Synthesis method

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

(3) Sub 14 synthesis method

Sub 14-3 (1 eq) and triphenylphosphine (2.5 eq) were dissolved in o-dichlorobenzene and refluxed for 24 h. 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 include, but are not limited to, the following.

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 include, but are not limited to, the following.

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)

Products Synthesis Examples: One of 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 ) And Sub 15 (1.1 eq.) Were added to toluene and Pd ₂ (dba) ₃ (0.05 eq.), PPh ₃ (0.1 eq.) And NaO t- Bu Reflux. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized.

(1) Product 16 Synthetic example

Pd ₂ (dba) ₃ , PPh ₃ , NaOt (dd) ₃ , and Pd ₂ (dba) were mixed in toluene after the addition of an ortho heteroaromatic compound (7.0 g, 20 mmol) and 2-bromo- -Bu are added, and the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.5 g (yield 65%).

(2) Product 32 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added after mixing the hetero atom compound (9.3 g, 20 mmol) and bromobenzene (3.8 g, 24 mmol) in toluene and the mixture was refluxed at 100 ° C for 24 hours . ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 7.4 g (yield: 68%).

(3) Product 60 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added to toluene after the addition of an orthoheterocyclic compound (6.5 g, 20 mmol) and 4- (4-bromophenyl) -2,6-diphenylpyrimidine (9.3 g, After the addition, the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 7.8 g (yield: 62%).

(4) Product 75 Synthetic Example

Pd ₂ (dba) ₃ , 4-bromo-2,7a-dihydro-1H-benzoimidazole (8.4 g, 24 mmol) PPh ₃ and NaOt-Bu, respectively, and the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 7.5 g (yield: 63%).

(5) Product 82 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ , NaOt (diborane), and Pd ₂ were prepared by mixing the toluene with 7.5 g, 20 mmol of the pentacyanohexane compound and 7.5 g -Bu are added, and the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 7.9 g (yield 65%).

(6) Product 103 Synthetic Example

Pd ₂ (dba) ₃ , Pd ₂ (dba) ₃ , and Pd ₂ (4-bromophenyl) -1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4 g, PPh ₃ and NaOt-Bu, respectively, and the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 8.1 g (yield: 63%).

(7) Product 105 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added to toluene, and then the mixture was refluxed with stirring at 100 ° C for 24 hours . ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 5.0 g (yield 70%).

(8) Product 200 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added to toluene after the addition of an orthoheterocyclic heteroaromatic compound (8.1 g, 20 mmol) and 2- (4-bromophenyl) -benzoimidazole (6.6 g, And the mixture is refluxed with stirring at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 7.4 g (yield 62%).

(9) Product 211 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added to toluene, respectively, after mixing the alkane heteroaromatic compound (9.0 g, 20 mmol) with 2- (4-bromophenyl) -4,6-diphenylpyrimidine (9.3 g, After the addition, the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 9.8 g (yield 65%).

(10) Product 225 Synthetic examples

Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added to toluene, respectively, after mixing the alkane heteroaromatic compound (9.0 g, 20 mmol) with 2- (4-bromophenyl) -4,6-diphenylpyrimidine (9.3 g, After the addition, the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 10.0 g (yield 66%).

(11) Product 231 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added to toluene, and then the mixture was stirred at 100 ° C. for 24 hours. Reflux. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 6.8 g (yield: 68%).

(12) Product 255 Synthetic example

Pd ₂ (dba) ₃ , Pd ₂ (dba) ₃ , and Pd ₂ (4-bromophenyl) -1-phenyl-2,7a-dihydro-1H-benzoimidazole (8.4 g, PPh ₃ and NaOt-Bu, respectively, and the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 9.4 g (yield 65%).

(13) Product 257 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added to toluene, and the mixture was refluxed at 100 ° C for 24 hours with stirring . ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 4.5 g (yield: 63%).

(14) Product 272 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ , NaOt (dd) ₃ , and Pd ₂ (dba) were mixed in toluene after the addition of an ortho heteroaromatic compound (7.0 g, 20 mmol) and 2-bromo- -Bu are added, and the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.5 g (yield 65%).

(15) Product 288 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added after mixing the hetero atom compound (9.3 g, 20 mmol) and bromobenzene (3.8 g, 24 mmol) in toluene and the mixture was refluxed at 100 ° C for 24 hours . ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 7.4 g (yield: 68%).

(16) Product 315 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ , and NaOt-Bu were added to toluene after the addition of an organic hetero compound (9.7 g, 20 mmol) and 2- (4-bromophenyl) -4,6-diphenylpyrimidine (9.3 g, After the addition, the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 12.7 g (yield 67%).

(17) Product 324 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ , NaOt (diborane), and Pd ₂ (dibromide) were mixed in toluene after the addition of an ortho heteroaromatic compound (9.7 g, 20 mmol) and 2-bromo-4,6- -Bu are added, and the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 11.5 g (yield 69%).

(18) Product 339 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added to toluene after the addition of the heteroatom (7.1 g, 20 mmol) and 2-bromo-4,6-diphenylpyrimidine (7.5 g, 24 mmol) And the mixture is refluxed with stirring at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 7.2 g (yield: 61%).

(19) Product 359 Synthetic Example

Pd ₂ (dba) ₃ , PPh ₃ , NaOt (diborane), and Pd ₂ (diborane) were mixed in toluene after the addition of an ortho heteroaromatic compound (7.5 g, 20 mmol) and 2- -Bu are added, and the mixture is refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 8.0 g (yield 62%).

Evaluation of manufacturing of organic electric device

[Experimental Example 1] (applied to a light emitting host)

An organic electroluminescent device was fabricated according to a conventional method using a compound obtained through synthesis as a luminescent host material in a light emitting layer. First, ITO layer (anode) formed on the glass substrate over the N ¹ - (naphthalen-2-yl) -N 4, N 4 -bis (4- (amino naphthalen-2-yl (phenyl)) phenyl) -N 1 - phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) was vacuum-deposited to form a hole injection layer having a thickness of 60 nm. Subsequently, 4,4-bis [ N - (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited on the hole injection layer to a thickness of 20 nm to form a hole transport layer . Next, a hole transport layer was doped with a compound of the present invention as a host material and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] as a dopant to a thickness of 95: Respectively. (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm to form a hole blocking layer , And tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF as 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 fabricating an organic electroluminescent device.

[Comparative Example 1]

An organic electroluminescent device was fabricated in the same manner as Experimental Example 1 except that the compound of the present invention was used as a luminescent host instead of the compound of the present invention to form a luminescent layer.

<Comparative Compound 1>

[Comparative Example 2]

An organic electroluminescent device was fabricated in the same manner as in Experimental Example 1, except that the compound of the present invention was used as a luminescent host instead of the compound of the present invention to form a luminescent layer.

&Lt; Comparative Compound 2 >

[Comparative Example 3]

An organic electroluminescent device was fabricated in the same manner as in Experimental Example 1, except that the compound of the present invention was used as a light emitting host to form a light emitting layer.

&Lt; Comparative Compound 3 >

In the embodiment, prepared as examples and comparative examples the organic was applied with a forward bias DC voltage to the electroluminescent device Photo Research (photoresearch) 's were measured and electroluminescence (EL) properties by PR-650, from the measurement result 300cd / m ² based on the luminance The T95 lifetime was measured using a life time measuring instrument manufactured by Mac Science. The following Table 17 shows the device fabrication and evaluation results for the examples and comparative examples in which the compounds according to the invention were applied. The organic electroluminescent devices manufactured according to Experimental Example 1 are shown in Examples 1 to 360.

As shown in the above table, the compound of the present invention exhibits higher luminous efficiency and longer lifetime than those of Comparative Examples 1 to 3, and particularly has a relatively low driving voltage, a high efficiency, a high lifetime . It is considered that the HOMO of the core is deepened by introducing the substituent into the backbone of the O atom hetero ring, and the HOMO value with the HTL is increased, so that the lifetime is increased by accelerating the hole mobility. Also, It is considered that the density is unevenly distributed, thereby exhibiting high efficiency.

The organic electroluminescent device using the material for an organic electroluminescent device of the present invention can be used as a luminescent host material to remarkably improve color purity, high luminescent efficiency and lifetime, and can be produced by mixing the compounds of the present invention with other organic layers, It is obvious that the same effect can be obtained even when it is used, for example, in a hole injection layer, a light emission assisting layer, an electron injection layer, an electron transport layer, and a hole injection layer.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

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

Claims (12)

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

In the above formulas,
X and Y are independently of each other S or O,
m is 1, n is 0, m is 1, n is 0,
R _{1 to} R ₁₀ are each a hydrogen atom, a heavy hydrogen atom, a C ₆ to C ₆₀ aryl group, a fluorenyl group, a C ₂ to C ₆₀ heterocyclic ring containing at least one hetero atom selected from O, N, S, Si and P (R ') (R "), a C ₁ to C ₅₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₃₀ alkoxy group, and a C ₆ to C ₃₀ aryloxy group With the proviso that one is -LN (R ') (R &quot;),
L is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P, and L (excluding a single bond) is selected from the group consisting of a nitro group, , One or more substituents selected from the group consisting of a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, a C ₂ to C ₂₀ heterocyclic group, a C ₁ to C ₂₀ alkoxy group, and an amino group , &Lt; / RTI &gt;
Ar ₁ represents a C ₂ to C ₆₀ heterocyclic group, a C ₆ to C ₆₀ aryl group, a fluorenyl group or -N (R ') group, a heterocyclic group having at least one heteroatom selected from O, N, S, Si and P, (R &quot;),
R 'and R "are each independently a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P, a C ₆ to C ₆₀ aryl group or a fluorenyl group Lt;
Wherein _{R 1 ~ R 10, Ar 1} , R ', R " is an aryl group when, each of which group deuterium, a halogen, a silane group, a boron, a germanium group, a cyano group, a nitro group, C ₁ ~ C ₂₀ of the alkylthio Substituted with C ₁ to C ₂₀ alkoxyl groups, C ₁ to C ₂₀ alkyl groups, C ₂ to C ₂₀ alkenyl groups, C ₂ to C ₂₀ alkynyl groups, C ₆ to C ₂₀ aryl groups, and deuterium A C ₂ to C ₂₀ aryl group, a C ₂ to C ₂₀ heterocyclic group, a C ₃ to C ₂₀ cycloalkyl group, a C ₇ to C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,
Wherein _{R 1 ~ R 10, Ar 1} , R ', R " in this case a heterocyclic group, each of which is heavy hydrogen, a halogen, a silane group, a cyano group, a nitro group, C ₁ ~ alkoxy group of C _20, C ₁ ~ C _A C ₂ to C ₂₀ alkenyl group, a C ₆ to C ₂₀ aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₂ to C ₂₀ heterocyclic group, a C ₃ to C ₂₀ A cycloalkyl group of C ₇ to C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,
Wherein _{R 1 ~ R 10, Ar 1} , R ', R " are fluorene when weather is, each of deuterium, a halogen, a silane group, a cyano group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkene Weather, C aryl group of ₆ ~ C _20, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₂ ~ C ₂₀ of the heterocyclic group and C ₃ ~ one or more substituents selected from the group consisting of a cycloalkyl group of C ₂₀ , &Lt; / RTI &gt;
When R ₁ to R ₁₂ are an alkyl group, it is preferably 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, An aryl group having ₆ to ₂₀ carbon atoms, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₂ to C ₂₀ heterocyclic group, a C ₇ to C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,
When R ₁ to R ₁₀ are alkenyl groups, they may be substituted by deuterium, a halogen, a silane 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, a 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 An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,
When R ₁ to R ₁₀ are alkoxyl groups, they may be substituted by 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 group substituted with deuterium, A C ₂ to C ₂₀ heterocyclic group, and a C ₃ to C ₂₀ cycloalkyl group, each of which may be substituted with at least one substituent selected from the group consisting of
When R ₁ to R ₁₀ are aryloxy groups, they may be substituted by 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 , A C ₂ to C ₂₀ heterocyclic group, and a C ₃ to C ₂₀ cycloalkyl group. The method according to claim 1,
The compound represented by the formula (1) is represented by the following formula (2) or (3):
&Lt; Formula 2 >< EMI ID =

Wherein X, Y, R ₁ -R ₁₀ , L and Ar ₁ are as defined in claim ₁ . The method according to claim 1,
Wherein one of R ₁ -R ₄ is -LN (R ') (R "). The method according to claim 1,
Lt; ₇ &gt; -R &lt; ₁₀ &gt; is -LN (R ') (R &quot;). The method according to claim 1,
-LN (R ') (R "), at least one of R' and R" is a fluorenyl group. The method according to claim 1,
Wherein at least one of R &lt; _{1 &gt;} -R &lt; ₁₀ &gt; is deuterium or a fluorenyl group. The method according to claim 1,
(L-Ar ₁ ) comprises a heterocycle. A compound characterized by being one of the following compounds:

. An organic electroluminescent device comprising a first electrode, a second electrode, and an organic material layer disposed between the first electrode and the second electrode,
The organic electroluminescent device according to any one of claims 1 to 8, wherein the organic layer comprises the compound of any one of claims 1 to 8. 10. The method of claim 9,
Wherein the organic layer includes a light emitting layer, and the compound is used as a host material of the light emitting layer. A display device including the organic electroluminescent device of claim 9; And
A controller for driving the display device; &Lt; / RTI &gt; 12. The method of claim 11,
Wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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