KR20200002020A - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

The present invention provides: a novel compound capable of improving luminous efficiency, stability, and lifespan of an element; an organic electric element using the same; and an electronic device thereof. By using the compound according to the present invention, it is possible to achieve high luminous efficiency, low driving voltage, and high heat resistance of the element, and it is possible to greatly improve color purity and lifespan of the element.

Description

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

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions.

On the other hand, it delays the penetration of metal oxides into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electric device, and is stable against Joule heating generated during driving of the device, that is, high glass transition. There is a need for development of a hole injection layer material having a temperature. In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials 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 lifetime of an element, an organic electric element 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 electronic device using the compound represented by the above formula and an electronic device thereof.

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

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

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

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are used to refer to the same components as much as possible even if they are shown in different drawings. In describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, the component may be directly connected to or connected to that other component, but there is another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

On the other hand, the terms "halo" or "halogen" as used herein are not described otherwise.

Fluorine, chlorine, bromine, and iodine.

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

As used herein, the term "alkenyl" or "alkynyl" has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto. The term "alkoxy group" used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise specified, but is not limited thereto.

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

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 3 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. In addition, it includes not only a single ring but also a heterocycle, and adjacent groups may be formed by bonding.

As used herein, the terms "heterocycloalkyl" and "heterocyclic group" include one or more heteroatoms, unless otherwise indicated, have a carbon number from 2 to 60, and include heterocycles as well as monocycles. Adjacent groups may be formed in combination. In addition, "heterocyclic group" may mean an alicyclic and / or aromatic including a heteroatom.

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 the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

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

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used herein refers to deuterium, halogen, amino, nitrile, nitro, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy groups, C ₁ to C ₂₀ alkylamine groups, C ₁ to C ₂₀ alkylthiophene groups, C ₆ to C ₂₀ arylthiophene groups, C ₂ to C ₂₀ alkenyl groups, 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 aryl alkenyl group, silane group, boron Group, germanium group, and C ₅ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but 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, a first electrode 110, and a second electrode 180 formed on a substrate 110. An organic material layer containing a compound represented by the formula (1) between) is provided. 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 layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.

In addition, although not shown, the organic electric device according to the present invention may further include a protective layer formed on one surface 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 hole injection layer 130, a hole transport layer 140, an electron transport layer 160, the electron injection layer 170, the host of the light emitting layer 150 or the material of the dopant or capping layer Can be used as

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

In addition, the organic material layer may be formed by using a variety of polymer materials, but not by a deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be prepared in a number of layers. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

In addition, the organic electroluminescent 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), a device for monochrome or white illumination.

Another embodiment of the present invention may include an electronic device including a display device including the organic electric element of the present invention described above, and a control unit for controlling the display device. In this case, 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 which concerns on one aspect of this invention is demonstrated.

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

[Formula 1]

In Chemical Formula 1,

R ₁ to R ₁₀ are each independently fused with hydrogen, deuterium, halogen, C ₆ ~ C ₆₀ aryl group, fluorenyl group, C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring C ₂ -C ₆₀ heterocyclic group including a ring group, O, N, S, Si and P heteroatoms, -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 It can be selected from the group consisting of, provided that when X is S or O, Y is S or If O, then R ₁ to R ₄ and R ₇ to R ₁₀ cannot both be hydrogen at the same time, for example, if X is S then R ₁ to R ₄ and R ₇ to R ₁₀ At least one of which may not be hydrogen, and when Y is O, at least one of R ₁ to R ₄ and R ₇ to R ₁₀ may not be hydrogen.

Or they may be joined to each other by ii) adjacent groups to form at least one ring, wherein the groups which do not form a ring are as defined in i).

Here, 'neighboring groups combine with each other to form at least one ring' means that R ₁ and R ₂ , R ₂ and R _3, and / or R ₃ and R ₄ combine with each other and at least one ring. It is meant to form a compound. At this time, since it is important that the adjacent groups are bonded to each other to form a ring, the scope of the present invention is not limited by what substituents and by what reaction the ring is formed. At this time, the ring is a 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 and the like).

The ring formed by bonding of adjacent groups among R ₁ to R ₁₀ may not only be a monocyclic or polycyclic aromatic ring or a hetero ring including at least one hetero atom, but also a fused aromatic ring and an aliphatic ring. For example, neighboring groups of R ₁ and R _{4 may} be bonded to each other to form an aromatic ring such as benzene, naphthalene, phenanthrene, and the like. For example, when R ₁ and R ₂ combine with each other to form a benzene ring, and R ₃ and R ₄ combine with 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, adjacent groups of R ₁ to R _{10 may} be bonded to each other to form a heterocycle such as thiophene, furan, pyridine, indole, quinoline, and the like, wherein the carbon number may be 2 to 60. In the case of a polycyclic ring, the ring may be fused to each other, a plurality of rings may not be fused to each other, or a ring in which the fused and non-fused forms are mixed.

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

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

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

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

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

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

When R ₁ to R ₁₂ , Ar ₁ , R ′ and R ″ are aryl groups, they are deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ ~ C ₂₀ alkylthio group, C ₁ ~ C ₂₀ Alkoxyl, C ₁ ~ C ₂₀ Alkyl, C ₂ ~ C ₂₀ Alkenyl, C ₂ ~ C ₂₀ Alkynyl, C ₆ ~ C ₂₀ Aryl , 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 May be substituted with one or more substituents selected from the group consisting of an arylalkyl group and an arylalkenyl group of C ₈ to C ₂₀ ,

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

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

And the R ₁ ~ R _1O is fused when ring group, which come alkylthio of deuterium, a halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro _{group, C 1 ~ C 20, C} 1 ~ C 20 alkoxy C ₁ ~ C ₂₀ Alkyl, C ₂ ~ C ₂₀ Alkenyl, C ₂ ~ C ₂₀ Alkynyl, C ₆ ~ C ₂₀ Aryl, C ₆ substituted with deuterium C ₂₀ -C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ May be substituted with one or more substituents selected from the group consisting of an arylalkyl group and an arylalkenyl group of C ₈ to C ₂₀ ,

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

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

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

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

On the other hand, the compound represented by Formula 1 may be represented by the following formula (2) or formula (3).

<Formula 2> <Formula 3>

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

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

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

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

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

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

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

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

In the above formula, X, Y, R ₁ ~ R 4, R ₅ , R ₆ , L and Ar ₁ are the same as defined in formula (1).

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

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

Synthesis Example

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

<Scheme 1>

[ Example  One]

One. Sub  1, synthesis

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

<Scheme 2>

(One) Sub  1-2 Synthesis Example

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

(2) Sub  1-3 Synthesis Example

The obtained Sub 1-2 was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to obtain the desired Sub 1-3.

(3) Sub  1-4 Synthesis Example

The obtained Sub 1-3, 1-iodo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 1-4.

(4) Sub  One Synthesis Example

The obtained Sub 1-4 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. 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 1.

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

TABLE 1

[ Example  2]

One. Sub  2 synthesis

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

<Scheme 3>

(One) Sub  2-2 Synthesis Example

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 the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product was obtained by concentrating the organic solvent to give the desired Sub 2-2 using column chromatography.

(2) Sub  2-3 Synthesis Example

Sub 2-2 and 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO 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. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. Water in the reaction was removed with anhydrous MgSO _4, and the product was filtered under reduced pressure, and then the organic solvent was concentrated to give the desired Sub 2-3 using column chromatography.

(3) Sub  2 Synthesis Example

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

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

TABLE 2

[ Example  3]

One. Sub  3 synthesis

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

<Scheme 4>

(One) Sub  3-1 Synthesis Example

Add 4-bromonaphthalen-1-ylboronic acid and (2-bromophenyl) (methyl) sulfane substituted with R ₇ to R ₁₀ , tetrakis (triphenylphophine) palladium (0) and potassium carbonate, THF (tetrahydrofuran) and water Add (3: 1) and stir at 70 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ , washed with water, a small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was recrystallized with CH ₂ Cl ₂ and hexane solvent. The desired Sub 3-1 was obtained.

(2) Sub  3-2 Synthesis Example

Sub 3-1 is dissolved in acetic acid, and hydrogen peroxide dissolved in acetic acid is dropped dropwise and stirred at room temperature for 6 hours. When the reaction was terminated by removing the acetic acid (acetic acid) using a reduced pressure device and separated by column chromatography to obtain the desired Sub 3-2.

(3) Sub  3-3 Synthesis Example

Add Sub 3-2 and trifluoromethanesulfonic acid thus obtained, and stir at room temperature for 24 hours. Then, slowly add water and pyridine (8: 1) to reflux for 30 minutes. Lower the temperature, extract with CH ₂ Cl ₂ and wipe 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 using column chromatography to obtain the desired Sub 3-3.

(4) Sub  3-4 Synthesis Example

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

(5) Sub  3 Synthesis Example

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

[ Example  4]

One. Sub  4 synthetic

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

Scheme 5

(One) Sub  4-1 Synthesis Example

Dissolve the 5-bromobenzo [b] naphtho [ 2,1-d] thiophene substituted with R _{7 ~ 10} in anhydrous THF, cooled the reaction to -78 ℃, was added dropwise n-BuLi (2.5 M inhexane) slowly and After that, the reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to obtain the desired Sub 4-1.

(2) Sub  4-2 Synthesis Example

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

(3) Sub  4 Synthesis Example

Sub 4-2 and triphenylphosphine obtained 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 then the concentrated product was separated by column chromatography to obtain the desired Sub 4.

[ Example  5]

One. Sub  5 synthetic

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

<Scheme 6>

(One) Sub  5-1 Synthesis Example

Dissolve 5-bromobenzo [b] naphtho [2,1-d] thiophene in dry THF, lower the temperature of the reaction to -78 ° C, slowly add dropwise n-BuLi (2.5 M inhexane), and then add the reaction to 0 ° C. Stirred for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the resulting product by concentration of the organic solvent was separated by column chromatography to give the desired Sub 5-1.

(2) Sub  5-2 Synthesis Example

Sub 5-1, 1-bromo-2-nitronaphthalene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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 using column chromatography to obtain the desired Sub 5-2.

(3) Sub  5 Synthesis Example

Sub 5-2 and triphenylphosphine obtained 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 then the concentrated product was separated by column chromatography to obtain the desired Sub 5.

[ Example  6]

One. Sub  6 synthetic

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

Scheme 7

(One) Sub  6-1 Synthesis Example

Dissolve 5-bromobenzo [d] naphtho [2,1-b] thiophene, 1-bromo-2-nitronaphthalene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ in dry THF and a small amount of water, and It was refluxed. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated by column chromatography to give the desired Sub 6-1.

(2) Sub  6 Synthesis Example

The obtained Sub 6-1 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. 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.

[ Example  7]

One. Sub  7 synthetic

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

Scheme 8

(One) Sub  7-1 Synthesis Example

Dissolve 5-bromobenzo [b] naphtho [2,1-d] thiophene in dry THF, lower the temperature of the reaction to -78 ° C, slowly add dropwise n-BuLi (2.5 M inhexane), and then add the reaction to 0 ° C. Stirred for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to give the desired Sub 7-1.

( 2) Sub  7-2 Synthesis Example

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

( 3) Sub  7 Synthesis Example

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

[ Example  8]

One. Sub  8 synthetic

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

Scheme 9

(One) Sub  8-1 Synthesis Example

Dissolve 5-bromobenzo [d] naphtho [2,1-b] thiophene in dry THF, lower the temperature of the reaction to -78 ° C, slowly add dropwise n-BuLi (2.5 M inhexane), and then add the reaction to 0 ° C. Stirred for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the resulting product by concentration of the organic solvent was separated by column chromatography to give the desired Sub 8-1.

( 2) Sub  8-2 Synthesis Example

The obtained Sub 8-1, 9-bromo-10-nitrophenanthrene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 8-2.

( 3) Sub  8 Synthesis Example

Sub 8-2 and triphenylphosphine obtained 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 then the concentrated product was separated by column chromatography to obtain the desired Sub 8.

[ Example  9]

One. Sub  9 synthetic

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

Scheme 10

( 1) Sub  9-1 Synthesis Example

2-bromodibenzo [b, d] thiophene substituted with R _{5 to 6} was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was zero. Stirred at &lt; RTI ID = 0.0 &gt; Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to give the desired Sub 9-1.

( 2) Sub  9-2 Synthesis Example

The obtained Sub 9-1, 1-bromo-2-nitronaphthalene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 9-2.

( 3) Sub  9 Synthesis Example

Sub 9-2 and triphenylphosphine obtained 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 9.

[ Example  10]

One. Sub  10 synthetic

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

Scheme 11

( 1) Sub  10-1 Synthesis Example

Of 3-bromodibenzo substituted with _{R 5 ~ 6 [b, d} ] thiophene was dissolved in anhydrous THF, cooled the reaction to -78 ℃, n-BuLi (2.5 M inhexane) After the dropwise slowly, and the reaction 0 Stirred at &lt; RTI ID = 0.0 &gt; Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to obtain the desired Sub 10-1.

( 2) Sub  10-2 Synthesis Example

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

( 3) Sub  10 Synthesis Example

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

[ Example  11]

One. Sub  11 synthetic

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

Scheme 12

( 1) Sub  11-1 Synthesis Example

2-bromodibenzo [b, d] thiophene substituted with R _{5 to 6} was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was zero. Stirred at &lt; RTI ID = 0.0 &gt; Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the resulting product by concentration of the organic solvent was separated by column chromatography to give the desired Sub 11-1.

( 2) Sub  11-2 Synthesis Example

Sub 9-1, 9-bromo-10-nitrophenanthrene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 11-2.

( 3) Sub  11 Synthesis Example

Sub 11-2 and triphenylphosphine obtained 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 then the concentrated product was separated using column chromatography to obtain the desired Sub 11.

[ Example  12]

One. Sub  12 synthetic

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

Scheme 13

( 1) Sub  12-1 Synthesis Example

Of 3-bromodibenzo substituted with _{R 5 ~ 6 [b, d} ] thiophene was dissolved in anhydrous THF, cooled the reaction to -78 ℃, n-BuLi (2.5 M inhexane) After the dropwise slowly, and the reaction 0 Stirred at &lt; RTI ID = 0.0 &gt; Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to obtain the desired Sub 12-1.

( 2) Sub  12-2 Synthesis Example

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

( 3) Sub  12 Synthesis Example

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

[ Example  13]

One. Sub  13 synthetic

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

Scheme 14

( 1) Sub  13-1 Synthesis Example

Dissolve 5-bromodinaphtho [1,2-b: 2 ', 1'-d] thiophene in dry THF, lower the temperature of the reaction to -78 ° C, and slowly add dropwise n-BuLi (2.5 M inhexane), The reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the resulting product by concentration of the organic solvent was separated by column chromatography to give the desired Sub 13-1.

( 2) Sub  13-2 Synthesis Example

Sub 13-1, 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 13-2.

( 3) Sub  13 Synthesis Example

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

[ Example  14]

One. Sub  14 synthetic

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

Scheme 15

( 1) Sub  14-1 Synthesis Example

After dissolving 5-bromodinaphtho [2,1-b: 1 ', 2'-d] thiophene in dry THF, lowering the temperature of the reaction to -78 ° C, and slowly dropwise adding n-BuLi (2.5 M inhexane), The reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction product with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to obtain the desired Sub 14-1.

( 2) Sub  14-2 Synthesis Example

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

( 3) Sub  14 Synthesis Example

Sub 14-2 and triphenylphosphine obtained 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 then the concentrated product was separated using column chromatography to obtain the desired Sub 14.

[ Example  15]

One. Sub  15 synthetic

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

Scheme 16

( 1) Sub  15-1 Synthesis Example

After dissolving 14-bromonaphtho [2,1-d] phenanthro [9,10-b] thiophene in dry THF, lowering the temperature of the reaction to -78 ° C and slowly adding n-BuLi (2.5 M inhexane) dropwise, The reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to give the desired Sub 15-1.

( 2) Sub  15-2 Synthesis Example

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

( 3) Sub  15 Synthesis Example

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

[ Example  16]

One. Sub  16 synthetic

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

Scheme 17

( 1) Sub  16-1 Synthesis Example

After dissolving 5-bromonaphtho [2,1-b] phenanthro [9,10-d] thiophene in dry THF, lowering the temperature of the reaction to -78 ° C, and slowly adding n-BuLi (2.5 M inhexane) dropwise, The reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to give the desired Sub 16-1.

( 2) Sub  16-2 Synthesis Example

Sub 16-1, 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 16-2.

( 3) Sub  16 Synthesis Example

Sub 16-2 and triphenylphosphine obtained 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 then the concentrated product was separated by column chromatography to obtain the desired Sub 8.

[ Example  17]

One. Sub  17 synthetic

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

Scheme 18

( 1) Sub  17-1 Synthesis Example

Dissolve the 8-bromobenzo [d] naphtho [ 1,2-b] thiophene substituted by R _{5 ~ 6} in anhydrous THF, cooled the reaction to -78 ℃, was added dropwise n-BuLi (2.5 M inhexane) slowly and After that, the reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to obtain the desired Sub 17-1.

( 2) Sub  17-2 Synthesis Example

Sub 17-1, 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 17-2.

( 3) Sub  17 Synthesis Example

Sub 17-2 and triphenylphosphine obtained 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 then the concentrated product was separated using column chromatography to obtain the desired Sub 17.

[ Example  18]

One. Sub  18 synthetic

Sub 18 may be synthesized by the reaction pathway of Scheme 19 below.

Scheme 19

( 1) Sub  18-1 Synthesis Example

Dissolve 9-bromobenzo [b] naphtho [1,2-d] thiophene substituted with R _{5 to 6} in dry THF, lower the temperature of the reaction to -78 ° C, and slowly add n-BuLi (2.5 M inhexane) dropwise. After that, the reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to give the desired Sub 18-1.

( 2) Sub  18-2 Synthesis Example

Sub 18-1, 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 18-2.

( 3) Sub  18 Synthesis Example

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

[ Example  19]

One. Sub  19 synthetic

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

Scheme 20

( 1) Sub  19-1 Synthesis Example

Dissolve the 12-bromobenzo [d] phenanthro [ 9,10-b] thiophene substituted by R _{5 ~ 6} in anhydrous THF, cooled the reaction to -78 ℃, was added dropwise n-BuLi (2.5 M inhexane) slowly and After that, the reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removing the water in the reaction with anhydrous MgSO ₄ and filtered under reduced pressure, the resulting product by concentration of the organic solvent was separated by column chromatography to give the desired Sub 19-1.

( 2) Sub  19-2 Synthesis Example

Sub 19-1, 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ obtained were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 19-2.

( 3) Sub  19 Synthesis Example

Sub 19-2 and triphenylphosphine obtained 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 19.

[ Example  20]

One. Sub  20 synthetic

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

Scheme 21

( 1) Sub  20-1 Synthesis Example

Dissolve the 11-bromobenzo [b] phenanthro [ 9,10-d] thiophene substituted with R _{5 ~ 6} in anhydrous THF, cooled the reaction to -78 ℃, was added dropwise n-BuLi (2.5 M inhexane) slowly and After that, the reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to obtain the desired Sub 20-1.

( 2) Sub  20-2 Synthesis Example

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

( 3) Sub  20 Synthesis Example

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

[ Example  21]

One. Sub  21 synthetic

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

Scheme 22

( 1) Sub  21-2 Synthesis Example

After dissolving the Sub 21-1 and R _{1 ~} a 1-bromo-2-nitrobenzene, Pd (PPh 3) is substituted by _{4 4,} K ₂ CO ₃ in dry THF and a small amount of water and the mixture was refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 21-2.

( 2) Sub  21 Synthesis Example

The obtained Sub 21-2 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. 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 desired Sub 21.

[ Example  22]

One. Sub  22 synthetic

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

Scheme 23

( 1) Sub  22-1 Synthesis Example

Dissolve the 5-bromo-11,11-dimethyl- 11H-benzo [a] fluorene substituted with R _{7 ~ 10} in anhydrous THF, cooled the reaction to -78 ℃, slowly n-BuLi (2.5 M inhexane) After dropwise addition, the reaction was stirred at 0 ° C for 1 h. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise, and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. After removal of water in the reaction product with anhydrous MgSO ₄ and filtration under reduced pressure, the product produced by concentration of the organic solvent was separated by column chromatography to obtain the desired Sub 22-1.

( 2) Sub  22-2 Synthesis Example

After dissolving the obtained Sub 22-1 and R _{1 ~} a 1-bromo-2-nitrobenzene, Pd (PPh 3) 4 is substituted by _4, K ₂ CO ₃ in dry THF and a small amount of water and the mixture was refluxed for 24 hours. After the reaction was completed, the temperature of the reactant 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. The resulting product was separated using column chromatography to obtain the desired Sub 22-2.

( 3) Sub  22 Synthesis Example

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

[ Example  23]

Sub  23 examples

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

TABLE 3

[ Example  24]

Products Synthesis Example

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

(One) Product  1-1 Synthesis Example

Scheme 24

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

( 2) Product  2-6 Synthesis Example

Scheme 25

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

( 3) Product  3-9 Synthesis Example

Scheme 26

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

( 4) Product  4-15 Synthesis Example

Scheme 27

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

( 5) Product  5-11 Synthesis Example

Scheme 28

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

( 6) Product  6-14 Synthesis Example

Scheme 29

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

( 7) Product  7-2 Synthesis Example

Scheme 30

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

( 8) Product  8-8 Synthesis Example

Scheme 31

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

( 9) Product  9-12 Synthesis Example

Scheme 32

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

( 10) Product  10-16 Synthesis Example

Scheme 33

Five-membered heterocyclic compound (6.9 g, 20 mmol) and 2- (4-bromophenyl) imidazo [1,2-a] pyridine (6.6 g, 24 mmol) were mixed with toluene, followed by Pd ₂ (dba) ₃ , PPh ₃ , NaOt- After adding Bu, respectively, it stirred at reflux for 24 hours at 100 degreeC. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallization to obtain 6.9 g (64% yield) of product 10-16.

( 11) Product  11-3 Synthesis Example

Scheme 34

After mixing five-membered hetero compounds (7.5 g, 20 mmol) and 2-bromopyridine (3.8 g, 24 mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added thereto, and the mixture was stirred at 100 ° C. for 24 hours. Reflux. After extracting with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give 6.2g (69% yield) of product 11-3.

( 12) Product  12-8 Synthesis Example

Scheme 35

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

( 13) Product  13-1 Synthesis Example

Scheme 36

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

( 14) Product  14-7 Synthesis Example

Scheme 37

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

( 15) Product  15-9 Synthesis Example

Scheme 38

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

( 16) Product  16-15 Synthesis Example

Scheme 39

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

( 17) Product  17-11 Synthesis Example

Scheme 40

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

( 18) Product  18-14 Synthesis Example

Scheme 41

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

( 19) Product  19-2 Synthesis Example

Scheme 42

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

( 20) Product  20-8 Synthesis Example

Scheme 43

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

( 21) Product  21-12 Synthesis Example

Scheme 44

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

( 22) Product  22-16 Synthesis Example

Scheme 45

Five-membered heterocyclic compound (6.9 g, 20 mmol) and 2- (4-bromophenyl) imidazo [1,2-a] pyridine (6.6 g, 24 mmol) were mixed with toluene, followed by Pd ₂ (dba) ₃ , PPh ₃ , NaOt- After adding Bu, respectively, it stirred at reflux for 24 hours at 100 degreeC. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give 6.8g (63% yield) of the product.

( 23) Product  23-3 Synthesis Example

Scheme 46

After mixing five-membered hetero compounds (7.5 g, 20 mmol) and 2-bromopyridine (3.8 g, 24 mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added thereto, and the mixture was stirred at 100 ° C. for 24 hours. Reflux. After extracting with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give 6.2g (69% yield) of the product.

( 24) Product  24-8 Synthesis Example

Scheme 47

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

( 25) Product  25-1 Synthesis Example

Scheme 48

After mixing five-membered hetero compounds (6.7 g, 20 mmol) and 2-bromo-4-phenylquinazoline (6.8 g, 24 mmol) in toluene, Pd ₂ (dba) ₃ , PPh ₃ and NaOt-Bu were added, respectively, and then 100 ° C. It is stirred at reflux for 24 hours. After extracting with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give the product 6.6g (61% yield).

( 26) Product  26-17 Synthesis Example

Scheme 49

Five-membered heterocyclic compound (6.7 g, 20 mmol) and 3- (2-bromoquinazolin-4-yl) -9-phenyl-9H-carbazole (10.8, 24 mmol) were mixed with toluene, followed by Pd ₂ (dba) ₃ , PPh ₃ , After NaOt-Bu was added, the mixture was stirred at reflux for 24 hours at 100 ° C. After extracting with ether and water, the organic layer was dried over MgSO ₄ , concentrated and the resulting organic material was silicagel column and recrystallized to give the product 8.2g (58% yield).

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

TABLE 4

Manufacturing Evaluation of Organic Electrical Device

[ Experimental Example  1] (phosphorescent green host)

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

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

[ Comparative example  One]

An organic light emitting diode was manufactured according to the same method as Experimental Example except for using Comparative Compound 2 as a host material when forming a light emitting layer.

<Comparative Compound 1>

[ Comparative example  2]

An organic light emitting diode was manufactured according to the same method as Experimental Example except for using Comparative Compound 3 as a host material when forming a light emitting layer.

<Comparative Compound 2>

[ Comparative example  3]

An organic light emitting diode was manufactured according to the same method as Experimental Example except for using Comparative Compound 3 as a host material when forming a light emitting layer.

Comparative Compound 3

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measured results were measured at a luminance of 300 cd / m ² . The T90 life was measured using a life measurement instrument manufactured by McScience.

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

TABLE 5

As can be seen from the results of the above table, the present invention shows higher luminous efficiency and higher lifetime than Comparative Examples 1 to 3, and in particular, a relatively low driving voltage, high efficiency and lifetime compared to Comparative Examples 2 and 3 Indicates. It is judged that the core has a deeper HOMO by introducing a substituent on the O-membered heterocyclic backbone, and has a suitable HOMO value with HTL, which increases the lifetime by accelerating hole mobility, and also the electron density of LUMO by the backbone substituent. By delocalizing, it is judged to exhibit high efficiency.

[ Experimental Example  2] (phosphorescence Red  Host)

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

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

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measured results were measured at a luminance of 300 cd / m ² . The T95 life was measured using a life measurement instrument manufactured by McScience.

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

TABLE 6

As can be seen from the results of Table 6, the organic electroluminescent device using the organic electroluminescent device material of the present invention can be used as a red light emitting layer material can significantly improve the high luminous efficiency, lifetime and color purity. In particular, when comparing the device results of Comparative Compound 2, Comparative Compound 3 and the compound of the present invention, the compound of the present invention, in which a substituent is introduced into the five-membered heterocyclic backbone and the quinazoline derivatives are connected, exhibits higher efficiency and longer lifetime. It was confirmed.

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

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

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein 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 protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted 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 (7)

A compound represented by the following formula (3):
<Formula 3>

In Chemical Formula 3,
X and Y are independently of each other S, O, C (R ₁₁ ) (R ₁₂ ) or Si (R ₁₁ ) (R ₁₂ ),
R ₁ to R ₁₀ are each independently of the other hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl groups; A C ₂ to C ₆₀ heterocyclic group including 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 aryloxy group Neighboring R ₁ and R ₂ , neighboring R ₂ and R ₃ , neighboring R ₃ and R ₄ , neighboring R ₇ and R ₈ , neighboring R ₈ and R ₉ , neighboring R ₉ and R ₁₀ At least one pair may combine with each other to form a benzene ring,
Provided that when X is S or O, except that R ₁ to R ₄ and R ₇ to R ₁₀ are both hydrogen at the same time,
L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; And a C ₂ ~ C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P,
Ar ₁ is a C ₆ ~ C ₆₀ An aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And fluorenyl group is selected from the group,
R ₁₁ and R ₁₂ are each independently hydrogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And it is selected from the group consisting of C ₁ ~ C ₅₀ Alkyl group,
R ′ and R ″ are each independently a heterocyclic group of C ₂ to C ₆₀ including at least one hetero atom of O, N, S, Si and P; C ₆ to C ₆₀ aryl group; and fluorene Diary,
Said aryl groups and heterocyclic groups are each deuterium, a halogen, a silane group, a cyano group, an alkyl group of a nitro group, C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ of, C ₂ - a C ₂₀ alkenyl group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, and O, N, S, C ₂ containing at least one hetero atom of Si and P It may be substituted with one or more substituents selected from the group consisting of ~ C ₂₀ heterocyclic group,
The fluorene group is a C ₆ ~ C ₂₀ substituted with heavy hydrogen, a halogen, a silane group, a cyano group, C ₁ ~ aryl group, a heavy hydrogen of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₆ ~ C ₂₀ of the It may be substituted with one or more substituents selected from the group consisting of an aryl group, and C ₂ ~ C ₂₀ heterocyclic group,
The arylene group and the fluorenylene group each of C ₆ ~ C ₂₀ aryl group; And it may be substituted with one or more substituents selected from the group consisting of C ₂ ~ C ₂₀ heterocyclic group including at least one hetero atom of O, N, S, Si and P. The method of claim 1,
Formula 3 is a compound, characterized in that represented by one of the following formula:
<Formula 14><Formula15>

<Formula 22><Formula23>

In Formula 14, Formula 15, Formula 22, and Formula 23, X, R ₅ , R ₆ , L, and Ar ₁ are the same as defined in claim ₁ . The method of claim 1,
Compound represented by the formula (3) is one of the following compounds:

. An organic electric element comprising a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode,
The organic material layer is an organic electroluminescent device comprising the compound of any one of claims 1 to 3. The method of claim 4, wherein
The organic material layer comprises an emission layer, the compound is an organic electroluminescent device, characterized in that used as a host material of the emission layer. Claim 4 display device comprising the organic electroluminescent element; And
And a controller for driving the display device. The method of claim 6,
The organic electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination.

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